KR101418134B1 - Polyamide-based laminated biaxially-stretched film, and vopor-deposited polyamide-based laminated resin film - Google Patents

Abstract

The present invention relates to a process for producing a mixture of xylylenediamine or a mixed xylylenediamine comprising metaxylylenediamine and p-xylylenediamine as main diamine components and an α, ω-aliphatic dicarboxylic acid component having 6 to 12 carbon atoms (B layer) composed mainly of an aliphatic polyamide resin is laminated on at least one side of a resin layer (A layer) composed mainly of a methacryloxy group-containing polyamide polymer having a main dicarboxylic acid component as a main component , A specific small pinhole number, and an oxygen permeability.

Description

[0001] The present invention relates to a polyamide-based laminated biaxially stretched film and a deposited polyamide-based laminated resin film,

INDUSTRIAL APPLICABILITY The present invention has excellent oxygen gas barrier properties, impact resistance and flexural fatigue resistance, and is useful as a packaging material for food packaging and the like, and has an effect of protecting contents from vibration or impact To a polyamide based laminated biaxially stretched film and an evaporated polyamide based laminated resin film suitable for various packaging applications.

Heretofore, a film made of a polyamide polymer containing xylylenediamine as a constituent has characteristics of being superior in oxygen gas barrier property and heat resistance, and strong in film strength, as compared with a film made of other polymer components.

On the other hand, an unstretched film or stretched film made of an aliphatic polyamide represented by nylon 6 or nylon 66 has excellent impact resistance and flexural fatigue resistance and is widely used as various packaging materials.

In the above-mentioned conventional film, when a film made of a polyamide polymer containing xylenediamine as an ingredient is used for a packaging material requiring bending fatigue resistance, There has been a problem that pinholes are likely to occur due to bending fatigue during transportation of goods. When a pinhole is generated in the packaging material of a product, it may cause contamination due to leakage of contents, generation of contents, mold, etc., leading to a decrease in the value of the product.

On the other hand, the film made of the latter aliphatic polyamide is excellent in film properties such as impact resistance and flexural fatigue resistance, but has a problem of poor oxygen gas barrier properties.

In order to solve these problems, there have been proposed a method in which a polyamide polymer comprising xylylenediamine as a constituent and an aliphatic polyamide or the like are melt-extruded by respective extruders, laminated and biaxially stretched (for example, Patent Documents 1 to 4).

However, the techniques described in these patent documents can not be regarded as satisfactory levels in terms of good product storage stability and protection against shock or bending such as transportation. In the method of Patent Document 2, in order to obtain a film satisfying good oxygen gas barrier property and flexural fatigue resistance, it is necessary to use a large amount of polyamide polymer having xylylenediamine as a constituent component, so that reduction in packaging and distribution costs is required This was not the preferred method. Patent Literature 3 discloses a method for producing a gas barrier resin layer comprising a gas barrier resin layer made of polyamide having xylylenediamine as a main component and a resin layer made of an aliphatic polyamide and a bending fatigue improving agent on at least one surface thereof, A film satisfying the barrier property and the bending fatigue resistance is disclosed. However, it is described that the ratio of the gas-barrier resin layer should be 40% or more in order to satisfy the gas barrier property. The inventors of the present invention evaluated the flexural fatigue resistance under severe conditions by using the film of Patent Document 3, but it was not satisfactory. Patent Document 4 discloses a film that combines both the anti-banding property and the flexural fatigue resistance by laminating a resin layer made of a mixed polyamide of an aliphatic polyamide and a semi-aromatic polyamide on at least one side of a resin layer made of an aliphatic polyamide and a thermoplastic elastomer However, even using this method, it was impossible to obtain a gas barrier film having flexural fatigue resistance. There is also a concern in the method described in the above publications in terms of prevention of deterioration of the contents due to vibration, impact, friction, etc. during transportation of the packaging material, which is particularly important in the form of food distribution in today's world .

Patent Document 1: JP-A-6-255054

Patent Document 2: Japanese Patent Application Laid-Open No. 2003-11307

Patent Document 3: Japanese Patent Application Laid-Open No. 2001-341253

Patent Document 4: Japanese Patent Application Laid-Open No. 2006-205711

The biaxially oriented polyamide based resin film is mainly used as a packaging material mainly because of excellent transparency, mechanical properties, gas barrier properties, impact resistance and pinhole resistance. Particularly, the contents requiring excellent impact resistance and pinhole resistance are used for so-called heavy bags, and they have been mainly used for bags larger than conventional objects such as rice flour. This large bag is about 30 cm in width and about 60 cm in length. Such a bag is usually produced by using a biaxially oriented polyamide based resin film as a base film, laminating various kinds of sealants (polyethylene, polypropylene, etc.) having heat sealability, and then heat- The shape of the sealing pouch is common. In general, the content of food or the like is often automatically charged immediately after the production of the bag, but the biaxially oriented polyamide based resin film has poor dimensional stability compared with the biaxially oriented polyester based resin film, There has been a problem in that the filling device does not hold the bag correctly and can not open the bag mouth, causing troubles such as leakage of the contents of food or the like. This phenomenon is conspicuous in the sequential biaxial stretching method, which is produced by stretching in the transverse direction after stretching in the longitudinal direction. Since such a phenomenon becomes more serious as the end portion of the film becomes larger, the portions near the film end portion and the central portion are cut in half, Therefore, a shrinkage percentage difference occurs, which is caused by the difference in the apparent dimension and the ordinal number.

As a technique relating to a method for producing a so-called bowing-suppressed film having uniform physical properties in the width direction, there has been proposed a method for producing a film having an unstretched sheet before transverse stretching, BACKGROUND ART As a technique related to a method of improving the bow shape of bowing observed in a bow shape after a straight line drawn by a felt pen or the like, for example, a method of dividing a heat fixing step into a first stage and a second stage (Patent Document 5); a method of providing a transition portion for adjusting the temperature between the transverse stretching process and the heat treatment process by simultaneous biaxial stretching (Patent Document 6); and a method of simultaneously There has been known a method in which biaxial stretching gradually raises the temperature from the transverse stretching step and the heat treatment step to the relaxation step and reaches the maximum temperature in the relaxation step (Patent Document 7). However, these methods are not suitable for reducing deformation of the actual film although the amount of bowing of the outer Boeing line is small. Although there is some correlation between the appearance of the bowing line and the actual deformation, it is insufficient to prevent curling of the bag.

Patent Document 5: Japanese Patent Application Laid-Open No. 7-108598

Patent Document 6: JP-A-10-44230

Patent Document 7: JP-A-10-235730

As a method for reducing the deformation of the film, there is a method in which a non-oriented polyamide film is stretched or relaxed by several percent in the longitudinal direction (flow direction), and then stretched in the transverse direction In a transverse stretching step in which a preheating temperature of 80 占 폚 or less and a two-step heat setting step are provided (Patent Document 8). As a result, the boiling shrinkage is 3% or less in all directions, and the flatness of the film is good and the dimensional change at the time of humidification is small. However, in this method, even if the respective shrinkage ratios are small, the difference in the shrinkage ratio in the width direction still remains, and the temperature is raised during high-speed processing, thereby causing a trouble due to the difference in shrinkage percentage. Further, as a method of reducing the physical property difference in the width direction, when a longitudinal direction stretching is performed, a temperature distribution is applied to the film temperature of the end portion, and the film is prevented from bowing when stretched in the transverse direction, As a result, the slope difference of the boiling shrinkage ratio is made small (Patent Document 9). However, this also fails to solve the phenomenon that the difference in the shrinkage ratio in the longitudinal direction is different in the width direction, and there is a problem in the high-speed machining as in Patent Document 8. Further, both ends of the stretched film are released from the clips of the tenter-type transversal stretching machine after the heat treatment after the transverse stretching and the relaxation treatment in the step of longitudinally stretching the non-oriented unoriented film and then transversely stretching, There is a method in which a reheat treatment is performed by adjusting a running direction tensile force, a reheat treatment temperature, and a treated wind speed by using a floating type heat treatment apparatus that blows hot air in an arc shape (Patent Document 10). However, even with this method, it is impossible to reduce the longitudinal heat shrinkage difference in the width direction, and there is a problem in that the length of the inside and the inside is different at one side (one side) when the bag is processed at high speed or cut in half .

Patent Document 8: Japanese Patent Application Laid-Open No. 7-256750

Patent Document 9: Japanese Patent Application Laid-Open No. 2002-172659

Patent Document 10: JP-A-10-296853

For this reason, a method of reducing the difference in heat shrinkage ratio (heat shrinkage ratio in the longitudinal direction of the film) in the width direction of the film in order to make the film passable in the post-processing step irrespective of the width of millrol , A continuous shielding plate is placed on a plenum duct (hot air blowing out port) arranged at upper and lower parts at regular intervals with respect to the advancing direction of the film in the heat fixing process of the film by the applicant, The temperature in the width direction of the film is increased from the center portion to the end portion so that the amount of relaxation of the end portion is approximated to the amount of relaxation at the center portion.

Patent Document 11: Japanese Patent Application Laid-Open No. 2001-138462

However, in the method in which only the continuous shielding plate is attached to the plenum duct (hot air blowing out portion) in the heat fixing treatment, the temperature hunting in the heat fixing zone becomes large, (That is, a portion where the difference in heat shrinkage ratio in the width direction of the film is large) is formed.

On the other hand, a production technique for producing a highly uniform polyamide-based resin biaxially stretched film has been studied, and as a result, it has been found that the film thickness, the physical properties such as the heat shrinkage and the refractive index are highly uniform, (For example, refer to Patent Document 12).

Patent Document 12: Japanese Patent Application Laid-Open No. 2007-130759

In the production of the above-mentioned polyamide based resin film roll, an unstretched sheet is formed by cooling and solidifying a sheet which is melt extruded from an extruder through a die on a moving cooling body such as a cooling roll (metal roll). In cooling and solidifying by such a cooling roll, if it is possible to directly adhere the polyamide-based resin sheet in a molten state onto the moving cooling body without interposing a thin air layer, quenching of the molten resin becomes possible, An undrawn sheet having a low degree of crystallinity can be obtained. Therefore, in the cooling and solidification by the cooling roll, a wire-shaped electrode is provided between the die and the moving cooling body in order to forcibly adhere the extruded molten sheet to the cooling body surface in a short time, so that static electricity (Hereinafter, a method of forming a bonded sheet by forced adhesion by the electrostatic charge is referred to as an electrostatic attraction forming method).

However, if the take-up speed of the sheet is slow, adhesion by electrostatic charge deposited on the surface of the sheet is possible. However, if the take-up speed is increased, it is impossible to make close contact with the electrostatic force, And the sheet thickness fluctuation increases, so that the cooling of the molten sheet is delayed to cause cooling unevenness, and a sheet having poor transparency with crystallization in progress and crystallization unevenness is obtained. Further, oligomer precipitation of the polyamide-based polymer occurs on the moving cooling body surface. Therefore, if the voltage applied to the electrode arranged between the die and the surface of the moving cooling body is increased in order to increase the amount of static charge deposited on the surface of the sheet, discontinuous arc discharge occurs between the electrode and the surface of the cooling body, The sheet material on the surface of the body is destroyed, and in severe cases, the surface coating of the cooling body is destroyed. Therefore, the voltage applied to the electrode can not be increased to a certain degree or more. Thus, in the conventional electrostatic attraction forming method, a highly uniform polyamide based resin film roll as in the above-described Patent Document 3 is manufactured with a sufficiently high film- It was impossible.

Furthermore, as described above, a laminated biaxially stretched film obtained by laminating a plurality of polyamide-based resins having different fluidity of a molten resin such as an aliphatic polyamide and the like with a polyamide polymer comprising xylylenediamine as a constituent is laminated in a molten state There is a problem that the adhesion stability between the molten resin sheet and the cooling body is particularly poor, and a continuous variation in thickness (crossing) occurs on the sheet.

Further, in general, a method is known in which a sealant layer is provided on a biaxially stretched polyamide film by a dry lamination method or an extrusion lamination method to obtain a heat sealable polyamide film laminate. The film laminate is subjected to printing, if necessary, and then the film laminate is molded into, for example, a bag shape, and the contents, for example, seasonings such as soybean paste and soy sauce, and foods containing water or chemicals such as soups and retort foods After that, the openings are thermally sealed to provide packaging products to general consumers.

There is a problem that when the moisture penetrates between the respective layers forming the polyamide film laminate having the sealant layer as described above, the adhesion between the layers is remarkably lowered. This may cause breakage if used as a packaging pouch. For example, when a retort food bag using a polyamide film laminate having a sealant layer is subjected to non-wastewater treatment or retort treatment, this problem is conspicuous and the bag becomes more prone to breakage. In addition, with the upgrading of packaged products, front multicolor printing is prevalent, which causes a problem of lowering the interlaminar adhesion due to the presence of the printing ink layer. Further, when the adhesive layer is interposed between the biaxially stretched polyamide film layer and the sealant layer, depending on the kind of the adhesive, the adhesive force is easily affected by the humidity, and particularly when the humidity-curable adhesive is used, , There is a problem that the adhesive force is largely changed depending on the season.

The present invention solves the problems of the conventional polyamide-based laminated biaxially stretched film, and is excellent in oxygen gas barrier property, impact resistance and flexural fatigue resistance, which are film qualities required for a packaging film, A polyamide-based laminated biaxially stretched film and a polyamide-based polyamide laminated film suitable for packaging applications that prevent deterioration or discoloration of the contents, and are also effective for prevention of product warpage due to vibration or shock during transportation, And to provide a laminated resin film.

In order to attain the more preferable aspect, it is preferable that the film passes through the heat treatment process at the time of post-processing of the film, and the film passes through the entire length of the roll irrespective of the condition of the post- And is excellent in oxygen gas barrier properties, impact resistance and flexural fatigue resistance, which are film qualities necessary for a packaging film, and can prevent deterioration or discoloration of contents when used as various packaging materials, Is intended to provide a polyamide-based laminated biaxially stretched film suitable for use in a mark, which is also effective for prevention of product warpage and protection of the quality of contents due to vibration or impact at the time of transportation.

A further object of the present invention is to provide a polyamide-based laminated biaxially stretched film which is excellent in water-resistance peeling resistance and water-heat peeling resistance when laminated, and which is suitable for packaging applications.

In order to achieve the above object, the present invention employs the following configuration.

1. A thermosetting resin composition comprising, as a main diamine component, a mixed xylylenediamine consisting of meta-xylylenediamine or meta-xylylenediamine and para-xylylenediamine and having an?,? - aliphatic dicarboxylic acid component having 6 to 12 carbon atoms (B layer) composed mainly of an aliphatic polyamide resin is laminated on at least one surface of a resin layer (A layer) composed mainly of a methacrylic acid group-containing polyamide polymer composed mainly of a dicarboxylic acid component and a poly The amide-based laminated biaxially stretched film is characterized by satisfying the following requirements (1) to (3).

(1) the ratio of the meta-xylylene group-containing polyamide polymer in the resin layer (A layer) containing the above-mentioned meta-xylylene group-containing polyamide polymer as a main component is 99% by weight or more, the thermoplastic elastomer is not added, Is added in a proportion of less than 1% by weight

(2) The laminate film of the polyamide-based laminated biaxially stretched film and the polyethylene film having a thickness of 40 占 퐉 was continuously fed at a rate of 40 cycles per minute in an atmosphere of a temperature of 23 占 폚 and a relative humidity of 50% using a gelboplex tester The number of pinholes when the bending test is performed for 2000 cycles is 10 or less

(3) The oxygen permeability at a temperature of 23 ° C and a relative humidity of 65% is 150 ml / m 2 · MPa · day or less

2. The laminated biaxially stretched polyamide laminate according to claim 1, wherein the laminated biaxially stretched polyamide laminate film and the laminated film of the polyethylene film having a thickness of 40 탆 have a peel strength of not less than 4.0 N / film.

3. The polyamide-based resin composition according to claim 1, wherein the thermoplastic elastomer is added to the resin layer (B layer) mainly composed of the aliphatic polyamide resin so that the mixing ratio is 0.5 wt% to 8.0 wt% Laminated biaxially stretched film.

4. The thermoplastic elastomer composition according to claim 1, wherein the thermoplastic elastomer is contained in an amount of 0.5 to 8.0% by weight and the methacrylic group-containing polyamide polymer is contained in an amount of 1.0 to 12.0% by weight in a resin layer (B layer) composed mainly of the aliphatic polyamide resin Of the polyamide-based laminated biaxially stretched film according to the second aspect.

5. The polyamide-based laminated biaxially stretched film according to the first or second aspect, wherein the polyamide-based laminated biaxially stretched film satisfies the following formula (I).

(Where x is the content (wt%) of the methacrylic group-containing polyamide polymer in the film, Pa is the oxygen permeability (ml / m 2 · MPa · day) of the film at a temperature of 23 ° C. and a relative humidity of 65% Represents the thickness (mm) of the film.

6. The polyamide-based laminated biaxially stretched film according to the first or second aspect, wherein the thickness of the layer A is 10% or more and 30% or less of the total thickness of the layer A and the layer B.

7. The polyamide-based laminated biaxially stretched film according to the first or second aspect, wherein the thickness of the film is 5 to 100 占 퐉.

8. The film according to any one of the items (4) and (6), wherein the difference Δnab between the refractive index in a direction forming an angle of 45 degrees with the winding direction of the film and the refractive index in a direction forming an angle of 135 degrees with respect to the winding direction is 0.003 or more and 0.013 or less, (5), wherein the polyamide-based laminated biaxially stretched film according to the first or second aspect of the present invention satisfies the following expression (5).

(4) For a film having a length in the width direction of the film of 80 cm or more, five samples were evenly divided in the width direction of the film, and five samples cut from the center in the width direction of each of the five When the difference between the maximum value and the minimum value of the HS160 is found, the difference is 0.15% or less when the HS160, which is the heat shrinkage rate in the film winding direction when heated for 10 minutes, is obtained.

(5) For all of the above five samples, HS160 should be 0.5% or more and 2.0% or less

9. A production method for producing the polyamide-based laminated biaxially stretched film according to the eighth aspect, which comprises a film forming step of forming an unstretched sheet by melt extrusion of a raw resin from an extruder, (6) to (8), wherein the biaxial stretching step is a biaxial stretching step of biaxially stretching the biaxially stretched film in the longitudinal direction and the transverse direction, Wherein the polyamide-based laminated biaxially stretched film is produced in the apparatus.

(6) A plurality of wide plenum ducts for extracting hot air are arranged so as to face up and down with respect to the traveling direction of the film

(7) A plurality of plenum ducts is provided with a shielding plate for shielding the hot air outlet

(8) The dimension of the shielding plate in the traveling direction of the film is adjusted to be substantially the same as the dimension of the outlet of each plenum duct in the traveling direction of the film, The dimensions of the film should be adjusted so as to become gradually longer with respect to the traveling direction of the film

10. A biaxially stretching process comprising stretching the film in the transverse direction after stretching the film in the longitudinal direction and providing an intermediate zone between the zone where the transverse stretching is performed and the heat fixation device, Wherein the polyamide-based laminated biaxially stretched film is a polyamide-based laminated biaxially stretched film.

11. The apparatus according to claim 1, characterized in that the open and closed teeth are divided into a plurality of heat fixing zones and the product of the temperature difference between the adjacent heat fixing zones and the wind speed difference is set to 250 DEG C · m / s or less Wherein said polyamide-based laminated biaxially stretched film is obtained by extrusion molding.

12. The polyamide-based laminated biaxially stretched film according to the first or second aspect, wherein the thickness unevenness is in the range of 3 to 10%.

13. A process for producing an unstretched sheet by melt-extruding a polyamide-based resin on a surface of a moving cooling medium and cooling the sheet to obtain an unstretched sheet, while suctioning the polyamide-based resin sheet in contact with the surface of the moving- A method for producing a polyamide-based laminated biaxially stretched film according to claim 12, wherein the corona discharge in the corona state is performed between the multi-needle electrode to which the direct current high voltage is applied and the molten resin sheet.

14. The polyamide-based laminated biaxially oriented film according to the first or second aspect, wherein an adhesive modifying resin made of a copolymer polyester is applied to the outermost surface of at least one surface of the film.

15. The application of the adhesive modifying resin as defined in any one of claims 1 to 13, wherein the co-extruded polyester resin aqueous dispersion contains particles of a grafted polyester and an aqueous solvent, Wherein the polyester has a graft portion formed by a radically polymerizable monomer comprising a polyester main chain and a radically polymerizable monomer having a hydrophilic group, wherein the grafted polyester particles have an average particle diameter of 500 nm or less , And the half-width of a 13 C-NMR signal of carbonyl carbon derived from the polyester main chain of the grafted polyester particles is 300 Hz or more.

16. A process for producing a mixture of xylylene diamine or meta-xylylenediamine and a mixed xylylenediamine comprising para-xylylenediamine as main diamine components and an α, ω-aliphatic dicarboxylic acid component having 6 to 12 carbon atoms (B layer) composed mainly of an aliphatic polyamide resin is laminated on at least one surface of a resin layer (A layer) composed mainly of a methacrylic acid group-containing polyamide polymer composed mainly of a dicarboxylic acid component and a poly Wherein the inorganic material is deposited on at least one side of the amide-based laminated biaxially stretched film, and the following requirements (9) to (10) are satisfied.

(9) The thermoplastic resin composition according to any one of the above items (1) to (3), wherein the ratio of the meta-xylylene group-containing polyamide polymer in the resin layer (A layer) composed mainly of the methacryloxy group-containing polyamide polymer is 99 wt.% Or more, Is added in a proportion of less than 1% by weight

(10) The laminated film of the deposited polyamide-based laminated resin film and the polyethylene film having a thickness of 40 탆 was continuously fed at a rate of 40 cycles per minute in an atmosphere of a temperature of 23 캜 and a relative humidity of 50% using a gelboplex tester The number of pinholes when the bending test is performed for 2000 cycles is 10 or less

(11) The oxygen transmission rate of the laminated film of the deposited polyamide-based laminated resin film and the polyethylene film having a thickness of 40 占 퐉 at a temperature of 23 占 폚 and a relative humidity of 65% is 50 ml / m.sup.2.multidot.day day or less.

(12) The laminated film of the deposited polyamide-based laminated resin film and the polyethylene film having a thickness of 40 탆 was continuously fed at a rate of 40 cycles per minute in an atmosphere of a temperature of 23 캜 and a relative humidity of 50% using a gelboplex tester , The oxygen permeability at a temperature of 23 캜 and a relative humidity of 65% is 100 ml / m 2 · MPa · day or less

17. The deposition polyamide based laminate according to the above 16, wherein the peel strength when the deposited polyamide based resin laminated film and the laminated film of the polyethylene film having a thickness of 40 占 퐉 are peeled off between the layers is 4.0 N / 15 mm or more Resin film.

18. The vapor-deposited polyamide according to the above-mentioned 16, wherein the thermoplastic elastomer is added to the resin layer (B layer) composed mainly of the aliphatic polyamide resin so as to have a mixing ratio of 0.5 wt% to 8.0 wt% Laminated resin film.

19. The thermoplastic resin composition according to any one of claims 1 to 7, wherein the thermoplastic elastomer is contained in an amount of not less than 0.5% by weight and not more than 8.0% by weight and the methacrylic group-containing polyamide polymer is contained in an amount of not less than 1.0% Is added so as to be a mixing ratio of the polyamide-based laminated resin film of the present invention.

20. The vapor-deposited polyamide based laminated resin film according to the above 16 or 17, wherein the thickness of the layer A is 10% or more and 30% or less of the total thickness of the layer A and the layer B.

21. The deposited polyamide based laminated resin film according to the above 16 or 17, wherein the thickness of the film is 8 to 50 mu m.

Wherein the inorganic substance is at least one kind of metal or nonmetal selected from aluminum, silicon, titanium, magnesium, zirconium, cerium, tin, copper, iron and zinc, or an oxide, nitride, The deposition polyamide based laminated resin film according to any one of claims 16 and 17, which is a sulfide.

23. The vapor-deposited polyamide laminated resin film according to the above 16 or 17, wherein the thickness of the film on which the inorganic substance is deposited is 5.0 nm or more and 200 nm or less.

Such a polyamide-based laminated biaxially stretched film and an evaporated polyamide-based laminated resin film of the present invention have excellent oxygen gas barrier properties, and are excellent in impact resistance and flexural fatigue resistance, and prevent deterioration or discoloration of contents And the content can be protected from bending fatigue caused by impact or vibration during transportation, and can be effectively used as various packaging materials.

In a more preferred embodiment of the polyamide based laminated biaxially stretched film of the present invention, the contents are used for applications called so-called watery foods, and they are sterilized by boiling and retort for sterilization of contents. This sterilization is carried out on the contents filled in bags produced by lamination in advance. Such a retort food bag is usually produced by laminating various sealants (polyethylene, polypropylene, etc.) having heat sealability using a biaxially oriented polyamide based resin film as a base film, then folding in half to heat- Called three-way sealing pouch or a form in which label printing is performed on the pouch.

In a more preferred embodiment of the polyamide based laminated biaxially stretched film of the present invention, it is excellent in water-exfoliating property and water-heat-peeling resistance, and can be effectively used as various packaging materials including retort food packaging.

Hereinafter, embodiments of the polyamide based laminated biaxially stretched film of the present invention will be described in detail.

The mixed diamine component of meta-xylylenediamine, or mixed xylylenediamine consisting of meta-xylylenediamine and p-xylylenediamine, which is used to constitute the A layer of the polyamide-based laminated biaxially stretched film of the present invention, And an alpha, omega-aliphatic dicarboxylic acid component having 6 to 12 carbon atoms as a main dicarboxylic acid component, wherein the para-xylylenediamine is 30% or more of the total xylylenediamine, , And the constitutional unit composed of xylylenediamine and aliphatic dicarboxylic acid is preferably at least 70 mol% in the molecular chain.

Examples of the meta-xylylene group-containing polyamide polymer to be used in the present invention include, for example, polymethylacrylene adipamide, polymethoxy-silane pimelamide, A homopolymer such as xylylene azelamide, polymethoxy silylene cevacamide, polymethoxy silylene dodecanediamide, and the like, and a combination of a methacrylic resin such as a meta-xylylene / paraxylylene adipamide copolymer, a meta-xylylene / para Xylylene pimelamide copolymers, metaxylylene / paraxylylene svelamide copolymers, meta xylylene / p-xylylene azelamide copolymers, metaxylylene / paraxylylene cevacamide Copolymers such as copolymers, meta-xylylene / p-xylylene dodecanediamide copolymers and the like, and homopolymers or copolymers thereof, may contain aliphatic diamines such as hexamethylenediamine, Aromatic dicarboxylic acids such as terephthalic acid, lactams such as epsilon -caprolactam, omega -aminocarboxylic acids such as aminoheptanoic acid, para-aminocarboxylic acids such as para-bis- (2-aminoethyl) And aromatic aminocarboxylic acids such as aminomethylbenzoic acid, and the like.

As the aliphatic polyamide resin used for constituting the B layer of the polyamide based laminated biaxially stretched film of the present invention, for example, nylon 6 containing ε-caprolactam as the main raw material may be mentioned. Examples of other polyamide resins include polyamide resins obtained by polycondensation of lactam, ω-amino acid, dibasic acid and diamine having three or more members (member rings). Specifically, examples of the lactam include enantolactam, caprylactam, lauryllactam, ω-amino acids such as 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminono Dicarboxylic acid, and 11-aminoundecanoic acid. Examples of dibasic acids include adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecadonic acid, hexadecadione acid, eicosanedioic acid, 2,2,4-trimethyladipic acid. Examples of the diamines include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, pentamethylenediamine, undecamethylenediamine, 2,2,4 (or 2,4,4) -trimethylhexamethylenediamine, cyclo Hexane diamine, and bis- (4,4-aminocyclohexyl) methane. Further, a small amount of an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, xylylenedicarboxylic acid, or a small amount of aromatic diamine such as meta Xylylenediamine, and the like. 6, 7, 11, 12, 6.6, 6.9, 6.11, 6.12, 6T, 6I, MXD6 (meta-xylylenediaminamide 6), 6 / 6.6, 6/12, 6 / 6T, 6 / 6I, 6 / MXD6. In addition, in the case of producing the polyamide-based laminated biaxially stretched film of the present invention, the above-mentioned polyamide resins can be used singly or in combination of two or more kinds.

Of the above-mentioned aliphatic polyamide resins, particularly preferred in the present invention are those having a relative viscosity in the range of 2.0 to 3.5. The relative viscosity of the polyamide-based resin influences the toughness and ductility of the obtained biaxially stretched film. When the relative viscosity is less than 2.0, the impact strength tends to be insufficient. On the contrary, Is more than 3.5, there is a tendency that the extensional biaxial stretchability is deteriorated by the increase of the stretching stress. The relative viscosity in the present invention refers to a value measured at 25 캜 using a solution of 0.5 g of polymer dissolved in 50 ml of 97.5% sulfuric acid.

[Nab]

The polyamide based laminated biaxially stretched film of the present invention is characterized in that the width DELTA nab of the mill rolls formed in a wide width (i.e., the refractive index in a direction forming an angle of 45 degrees with the winding direction of the wound film and the winding direction of the wound film And the difference (absolute value) of the refractive index in the direction forming an angle of 135 degrees) is preferably 0.003 or more and 0.013 or less. That is, in the case of a film in which DELTA nab is less than 0.030, there is no problem of the above-mentioned "deformation (that is, difference in physical properties in the width direction)". Further, in the case of a film in which DELTA nab is 0.013 in the up-and-down direction, it is difficult to adjust the difference in heat shrinkage ratio or the like so as to satisfy the requirements of the present invention. In the present invention, " DELTA nab " means DELTA nab at a position within 50 mm from the edge of one end of the film and within 50 mm from the edge of the other end, and the larger one of the two values It says.

[HS160]

 In the polyamide based resin film of the present invention, when the sample cut base portion is set by a method described later, in each cut base portion, a position within 50 mm from the one end edge in the width direction of the film, And HS160, which is a heat shrinkage ratio in the film winding direction when the sample was heated at 160 DEG C for 10 minutes, was obtained. When the difference in heat shrinkage ratio, which is the difference between HS160 and HS160, was obtained , And the difference in heat shrinkage ratio in all the cut-off portions is preferably 0.15% or less.

The polyamide-based laminated biaxially stretched film of the present invention can be obtained by laminating two or more layers of A / B (two kinds of two layers) or B / A / B (two kinds of three layers) In the case of the resin layer in which the B layer and the C layer are different from each other in the main layer). On the side of the curl, the B / A / B configuration which is a symmetrical layer configuration is particularly preferred. In the following description, among the respective layers constituting the laminated film, a layer mainly composed of a resin mainly composed of a methacryloxy group-containing polyamide polymer, which is not located on the outermost side (that is, B (A layer in the case of the A / B layer / A / B layer or B / A / C layer), and a thin layer in the two- Layer A) is referred to as a core layer. Further, the outermost layer (i.e., B and C layers in the case of B / A / B or B / A / C layers) mainly composed of an aliphatic polyamide resin and a two- (That is, the B layer in the case of the thick B layer and the A / B layer structure of the thin A layer) is referred to as a skin layer.

The ratio of the thickness of each layer of the polyamide based laminated biaxially stretched film is preferably 10% or more, more preferably 15% or more, and particularly preferably 18% or more, as the lower limit of the thickness ratio of the A layer. The upper limit of the thickness ratio of the A layer is preferably 30% or less, more preferably 25% or less, particularly preferably 23% or less. The lower limit of the thickness ratio of the B layer or the B layer and the C layer is preferably 70% or more, more preferably 75% or more, and particularly preferably 77% or more. The upper limit of the thickness ratio of the B layer or the B layer and the C layer is preferably 90% or less, more preferably 85% or less, particularly preferably 82% or less. In the case of the two-kind three-layer B / A / B configuration, the thickness ratio of the B layer as the surface layer means the sum of the thickness ratio of both surface layers, The thickness ratio of the B layer and the C layer as the surface layers means the sum of the thickness ratio of both surface layers. When the thickness ratio of the A layer exceeds 30%, the flexural fatigue resistance is deteriorated and the pinhole tends to increase, which is not preferable. On the other hand, if the thickness ratio of the A layer is less than 10%, the gas barrier property tends to be deteriorated.

As the resin for forming the skin layer, a thermoplastic elastomer may be added, if necessary, with an aliphatic polyamide resin as a main component. The lower limit of the amount of the thermoplastic elastomer added to the aliphatic polyamide resin is preferably 0.5% by weight or more, more preferably 1.0% by weight or more, particularly preferably 2.0% by weight or more. The upper limit is preferably 8.0 wt% or less, more preferably 7.0 wt% or less, and particularly preferably 6.0 wt% or less. If the addition amount of the thermoplastic elastomer is less than 0.5 wt%, the effect of improving the flexural fatigue resistance may not be obtained. On the other hand, if the addition amount of the thermoplastic elastomer is more than 8.0 wt%, it may not be suitable for packaging applications such as foods requiring high transparency (haze). The resin forming the skin layer may be filled with a thermoplastic elastomer, an aliphatic polyamide resin, or other resin, if necessary, and may be filled with a lubricant, an antiblocking agent, a heat stabilizer, an antioxidant, It is also possible to charge the photocatalyst, impact resistance improver and the like.

Examples of the thermoplastic elastomer used in the present invention include polyamide resins such as nylon 6 and nylon 12 and polyamides such as block or random copolymers with PTMG (polytetramethylene glycol) or PEG (polyethylene glycol) Based elastomer such as a styrene-based elastomer, an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, a copolymer of ethylene and butene, a copolymer of styrene and butadiene, and an ionomer of an olefinic resin such as an ethylene- Can be used.

Further, in the polyamide based laminated biaxially stretched film of the present invention, a methacrylic group-containing polyamide polymer may be added to the resin constituting the skin layer, if necessary. By adding the methacrylic group-containing polyamide polymer to the resin constituting the skin layer, it is possible to prevent delamination between the aliphatic polyamide resin constituting the skin layer and the thermoplastic elastomer interface, Baginess) can be improved. When the meta-xylylene group-containing polyamide polymer is added, the upper limit of the addition ratio is preferably 12.0 wt% or less, more preferably 10.0 wt% or less, and particularly preferably 8.0 wt% or less. When the addition amount of the meta xylylene group-containing polyamide polymer exceeds 12.0 wt%, the impact resistance as a film may be impaired. The lower limit of the amount of the meta-xylylene group-containing polyamide polymer to be added is preferably 1.0% by weight or more, more preferably 2.0% by weight or more, and particularly preferably 3.0% by weight or more. If the addition amount of the meta-xylylene group-containing polyamide polymer is less than 1.0% by weight, the effect of improving the anti-magnetic property of the packaging material using the film may not be sufficiently obtained.

On the other hand, it is necessary that the resin forming the core layer contains a methacryl-containing polyamide polymer. If necessary, other resins such as a polyamide-based resin or a thermoplastic elastomer can be mixed. In the case where a resin other than the methacryl-containing polyamide polymer is mixed into the resin forming the core layer, It is necessary to make the content ratio of the polyamide polymer 99% by weight or more, preferably 100% by weight, and the content of other resins to be less than 1% by weight in order to obtain good gas barrier properties. Particularly, when the thermoplastic elastomer is mixed, it is necessary to make the content of the thermoplastic elastomer less than 1% by weight. As described above, a skin layer containing a relatively soft aliphatic polyamide resin as a main component is provided on the outer side of the core layer containing a hard meta-xylylene-containing polyamide polymer as a main component, and the skin layer is filled with a thermoplastic elastomer , It is possible to exhibit good gas barrier properties by the meta-xylylene-containing polyamide polymer and to exert an excellent effect of improving the flexural fatigue resistance by the thermoplastic elastomer and the polyamide-based resin.

If necessary, the resin forming the core layer may be filled with a lubricant, an antiblocking agent, a heat stabilizer, an antioxidant, an antistatic agent, an anti-light agent, and an impact resistance improver.

The polyamide based laminated biaxially stretched film of the present invention is obtained by laminating a laminated film of a polyethylene film having a thickness of 40 占 퐉 in an atmosphere of a temperature of 23 占 폚 and a relative humidity of 50% by using a gelboplex tester in the following manner, It is preferable that the number of pinholes is 10 or less when a bending test of 2000 cycles is continuously performed at a speed of 40 cycles per minute. Of course, the most preferable number is zero.

A method of measuring the pinhole number is as follows. A film cut to a predetermined size (20.3 cm x 27.9 cm) laminated with a polyolefin film or the like is conditioned for a predetermined time at a predetermined temperature, and then the rectangular test film is rolled to form a circle having a predetermined length Normally. Then, both ends of the cylindrical film were fixed to the outer circumference of the disk-shaped fixing head of the gelboplex tester and the outer circumference of the disk-shaped movable head, respectively, and the movable head was moved in the direction of the fixed head, (4.40 cm) while approaching a predetermined length (7.6 cm) along the axes of both heads, and after advancing a predetermined length (6.4 cm) without continuing to rotate, their operation is performed in the reverse direction, The bending test of one cycle of returning to the initial position is continuously repeated for a predetermined cycle (2000 cycles) at a predetermined speed (40 cycles per minute). Then, the number of pinholes occurring in a predetermined range (497 cm 2) except the fixed head of the tested film and the portion fixed to the outer periphery of the movable head is measured.

Due to the fact that the number of pinholes is in the above range, the polyamide-based laminated biaxially stretched film of the present invention is not easily damaged by vibration or impact when transporting the gas barrier packaging material using the film, It is possible to effectively exhibit the effect of preventing leakage of contents or deterioration of quality. It is more preferable that the number of pinholes is 8 or less, and it is particularly preferable that the number of pinholes is 6 or less.

As means for reducing the number of pinholes of the polyamide based laminated biaxially stretched film of the present invention to 10 or less, it is preferable that the resin layer (A layer) containing a methacrylic group-containing polyamide polymer as a main component is made as thin as possible At the same time, it can be achieved by suitably containing a thermoplastic elastomer in a resin layer (layer B) mainly composed of an aliphatic polyamide resin.

The polyamide-based laminated biaxially stretched film of the present invention preferably has an oxygen permeability of 150 ml / m 2 24 H 占 a a or less at a temperature of 23 占 폚 and a relative humidity of 65%.

Since the oxygen permeability falls within the above range, the polyamide-based laminated biaxially stretched film of the present invention effectively exhibits the effect of preventing degradation of the quality of the contents when the gas barrier packaging material using the same is stored for a long period of time . The oxygen permeability is more preferably 130 ml / m < 2 > .24H · MPa or less, and particularly preferably 110 ml / m < 2 > The lower limit of the oxygen permeability in the present invention is about 60 ml / m < 2 > 24H. MPa from the limit of the gas barrier properties of the methacryl group-containing polyamide polymer itself.

As a means for reducing the oxygen permeability of the polyamide based laminated biaxially stretched film of the present invention to 150 ml / m < 2 > 24H · MPa or less, it is preferable that the resin layer (A) containing a methacryloxy group-containing polyamide polymer as a main component Layer and the thickness of the A layer is appropriately adjusted within a range of 10 to 30% of the entire thickness of the film.

The polyamide-based laminated biaxially stretched film of the present invention contains x (% by weight) representing the content of the methacryloxy group-containing polyamide polymer in the film, t (mm) representing the thickness of the film, Pa (ml / M 2 · MPa · day) satisfies the relationship of the following formula (I) because it satisfies the gas barrier property, the pinhole property and the laminate adhesion property at a high level. By satisfying the relationship of the formula (I), it is possible to obtain an economically excellent film having a gas barrier property with a low content of MXD6 in the film, and a reduction in flexural fatigue resistance being small.

It is preferable that x is in the range of 5 to 50 (wt%) and t is in the range of 0.008 to 0.050 (mm) (8 to 50 탆).

When a resin having a relatively high gas barrier property such as a methacrylic group-containing polyamide polymer is mixed with another resin having relatively low gas barrier properties such as an aliphatic polyamide resin, two types of resins are dispersed and homogenized , And acts to inhibit the formation of an effective gas barrier structure. As the mixing ratio increases, and the degree of mixing and homogenization increases, the gas barrier property tends to decrease. Further, in the case where the single layer of the gas barrier resin and the single layer of the other resin are laminated in a state in which they are not completely mixed, the laminated film has the best gas barrier property, but in the case of lamination of the molten resin, Minute fluctuation occurs at the interface of the resin layer of the resin layer and the gas barrier property is slightly lowered in some cases.

The inventors of the present invention have found that a polyamide laminated film satisfying the relationship of the formula (I) effectively exhibits gas barrier properties at a small ratio of the gas barrier resin. That is, since the polyamide based resin laminated biaxially stretched film of the present invention satisfying the relationship of the formula (I) exhibits effective gas barrier properties of the methacrylic group-containing polyamide and maintains flexibility , The impact resistance is less likely to be deteriorated.

If the content of the meta-xylylene group-containing polyamide polymer is increased, it is necessary to increase the content of the meta-xylylene group-containing polyamide polymer in order to compensate, for example, It is necessary to increase the addition amount of the thermoplastic elastomer in order to compensate for the decrease in pinhole resistance.

As means for satisfying the relationship of the formula (I), it is preferable that the A layer containing a methacrylic group-containing polyamide polymer as a main component does not contain any other resin, the ratio of other resins is minimized, By adjusting the mixing method or the kneading condition so as not to mix the two components as much as possible.

The polyamide based laminated biaxially stretched film of the present invention preferably has a peel strength of not less than 4.0 N / 15 mm when a laminated film with a polyethylene film or the like is peeled off between the layers.

The outline of the method of measuring the peel strength is as follows. The laminated film of the polyamide-based laminated biaxially stretched film layer and the polyolefin film layer was peeled off at a peel strength of 180 degrees at a temperature of 23 deg. C and a relative humidity of 65% under the conditions of a width of 15 mm and a length of 200 mm and a laminate film laminated with a polyolefin film, The strength at the time of peeling is measured.

Since the peel strength is in the above range, the polyamide-based laminated biaxially stretched film of the present invention is excellent in peeling and fine hole piercing caused by vibration, impact, and the like when transporting the gas- It is possible to effectively exhibit the effect of preventing the deterioration of exposure and quality of the contents. It is particularly preferable that the peel strength is 5.0 N / 15 mm or more, and the peel strength is 5.5 N / 15 mm or more. The upper limit of the peel strength in the present invention depends on the strength of the adhesive strength between the adhesive resin and the film, and the upper limit is practically about 8.0 N / 15 mm.

As a means for setting the peel strength of the polyamide based laminated biaxially stretched film of the present invention to 4.0 N / 15 mm or more, it is preferable to increase the interaction between the aliphatic polyamide resin constituting the skin layer and the thermoplastic elastomer interface to be added, It is effective to prevent. As a concrete means, it is effective to appropriately add the methacrylic group-containing polyamide polymer in the skin layer containing the aliphatic polyamide resin as a main component within the range of 1.0 to 12.0 wt%. As a result, the effect of alleviating the deformation caused by the orientation that occurs during stretching of the film is enhanced and the peeling strength is increased between the layers of the aliphatic polyamide resin and the thermoplastic elastomer. As other means, there is a method of increasing the degree of melt-kneading in order to enhance the interaction between the thermoplastic elastomer and the aliphatic polyamide resin, a method of introducing a functional group for enhancing compatibility with the aliphatic polyamide into the thermoplastic elastomer, The peeling strength can be further increased by a method such as adjusting the magnification and the heat fixing temperature appropriately.

The object of the present invention is to provide a polyamide laminated biaxially stretched film which shares the above characteristics well in terms of preservation of the contents of the packaging material using the polyamide film and protection against shock, . The polyamide-based laminated biaxially stretched film of the present invention exhibits excellent elastic restoring force under room temperature or low temperature environment, exhibits excellent impact resistance and flexural fatigue resistance, and has good processability such as printing and lamination, It is a laminated biaxially stretched film suitable as a packaging material.

The thickness of the polyamide-based laminated biaxially stretched film of the present invention is not particularly limited, but when it is used as a packaging material, the thickness is preferably 5 to 100 탆, more preferably 8 to 50 탆 And particularly preferably 10 to 30 탆.

The thickness unevenness of the polyamide based laminated biaxially stretched film of the present invention is preferably in the range of 3% or more and 10% or less. The thickness irregularity is more preferably 8% or less, and particularly preferably 6% or less. Further, it is difficult to make the thickness unevenness to be less than 3% as an ordinary production technique.

The polyamide based laminated biaxially stretched film of the present invention can be produced by the following production method. For example, a method in which a polymer constituting each layer is melted using respective extruders and co-extruded from one die, a method in which a polymer constituting each layer is melted and extruded into a film separately and then laminated And a method in which these are combined. It is preferable to melt the polymers constituting each layer by using respective extruders, and to produce by co-extrusion from one die. The stretching method can be produced by a method such as a flat-type sequential biaxial stretching method, a flat-type simultaneous biaxial stretching method, and a tubular method, and a flat-type sequential biaxial stretching method is preferable. Here, the production of a film by the melt co-extrusion method and the flat-type sequential biaxial stretching method will be described as an example.

The raw material resin was melt-extruded from two extruders by a co-extrusion method, and was joined by a feed block, extruded from a T-die into a film form, fed to a cooling roll and cooled to obtain two kinds of layers B, A and B To obtain an unstretched film having a three-layer laminated structure. At that time, the melting temperature of the resin in each extruder is arbitrarily selected within the range of the melting point + 10 ° C to 50 ° C of the resin constituting each layer. From the viewpoint of uniformity of the film thickness and prevention of deterioration of the resin, in the case of the layer A composed of a methacrylic acid group-containing polyamide polymer, the temperature is preferably in the range of 245 to 290 DEG C, preferably 255 to 280 DEG C, Layer is preferably in the range of 230 to 280 ° C, and more preferably 250 to 270 ° C. The obtained non-stretched sheet is introduced into a roll-type longitudinal stretching machine and is stretched in the longitudinal direction at a temperature in the range of 65 to 100 캜, preferably 80 to 90 캜, by 2.0 to 5.0 times, preferably 3.0 to 4.0 Followed by introduction into a tenter-type transverse stretching machine, followed by transversely stretching at a temperature in the range of 80 to 140 ° C, preferably 100 to 130 ° C, at 3.0 to 6.0 times, preferably 3.5 to 4.0 times, Heat setting at a temperature in the range of 0 to 230 ° C, preferably 200 to 220 ° C, and relaxation treatment in the range of 0 to 8%, preferably 2 to 6%, to obtain a polyamide-based laminated biaxially stretched film.

In the present invention, the polyamide-based laminated biaxially stretched film satisfying the requirements of particular? Nab and the requirements (4) and (5) of the claims can be produced, for example, by the following production method. An unoriented film (unstretched laminated film or unstretched laminated sheet) obtained by melt extrusion of a polyamide based resin chip as a raw material is biaxially stretched in the longitudinal direction (longitudinal direction) and transverse direction (width direction) And then heat-fixing by the method described later.

The raw material resin is melt-extruded from two extruders by a co-extrusion method. The raw material resin is melt-extruded from the two extruders, merged by a feed block, melt extruded from a T die into a sheet and supplied to a cooling roll to be cooled. Layer laminate structure of a two-kind three-layer structure. At that time, the melting temperature of the resin in each extruder is arbitrarily selected within the range of the melting point + 10 ° C to 50 ° C of the resin constituting each layer. From the viewpoints of the uniformity of the film thickness and the prevention of the deterioration of the resin, in the case of the layer A composed of the methacryloxy group-containing polyamide polymer, the temperature is in the range of 245 to 290 ° C, preferably 255 to 280 ° C, And in the case of the B layer, it is preferably in the range of 230 to 280 캜, preferably 250 to 270 캜.

Further, a known method can be applied to quench the sheet-like molten material while closely adhering to the rotary cooling drum to form an unstretched sheet. For example, a method of using an air knife or a method of applying static electricity to a sheet- And the like can be preferably applied. In the latter method, the latter is preferably used.

As a method for cooling the air surface of the sheet material, a known method can be used. For example, a method of contacting the sheet surface with a cooling liquid in a tank (tank), a method of spraying A method of applying a liquid that evaporates) or a method of spraying a high-speed air stream to cool it may be used in combination. The thus obtained unstretched sheet is stretched in the biaxial direction to obtain a film.

As a method of stretching the film in the biaxial direction, there can be mentioned a method of stretching the obtained non-stretched sheet in the longitudinal direction by a roll or tenter type stretching machine and then stretching in the width direction orthogonal to the stretching direction in the first stage . The stretching temperature in the longitudinal direction is preferably 45 to 100 ° C, and the stretch ratio in the longitudinal direction is preferably 2.5 to 4.0 times, more preferably 3.0 to 3.6 times. If the stretching temperature in the longitudinal direction is less than 45 캜, the film tends to break, which is not preferable. On the other hand, if it exceeds 100 ° C, the thickness of the obtained film is not uniform. If the stretching ratio in the longitudinal direction is less than 2.5 times, the flatness of the obtained film becomes poor, which is not preferable. On the other hand, if it exceeds 4.0 times, the orientation in the longitudinal direction becomes strong, and the frequency of breakage in the transverse direction increases, which is not preferable.

In the case of stretching in the width direction, the stretching temperature is preferably 8 to 210 캜, more preferably 100 to 200 캜. If the stretching temperature in the transverse direction is less than 80 캜, the film tends to be broken, which is not preferable. On the other hand, if it exceeds 210 DEG C, thickness irregularity of the obtained film tends to deteriorate, which is not preferable. The draw ratio in the width direction is preferably 3.0 to 5.0 times, more preferably 3.5 to 4.5 times. When the stretching magnification in the width direction is less than 3.0 times, unevenness in the thickness of the obtained film is deteriorated, which is not preferable. If the stretching magnification in the width direction exceeds 5.0 times, the frequency of breakage in the stretching increases, which is not preferable.

Subsequently, heat fixing processing is performed. The temperature of the heat fixation treatment step is preferably 180 ° C or more and 230 ° C or less. If the temperature of the heat setting treatment is less than 180 캜, the absolute value of the heat shrinkage becomes large, which is not preferable. On the other hand, if the temperature of the heat fixing treatment is higher than 230 占 폚, the film tends to become yellow, mechanical strength tends to weaken, and the frequency of breakage increases, which is not preferable. A preferred method for fixing the heat will be described later.

It is effective to control the heat shrinkage rate, particularly the heat shrinkage rate in the width direction, by narrowing the front side of the guide rail of the wave guide by the heat fixing process and performing relaxation treatment. The temperature at which the relaxation treatment is carried out can be selected from the range of from the heat fixation treatment temperature to the glass transition temperature Tg of the polyamide based resin film, but is preferably -10 ° C to Tg + 10 ° C (heat fixation treatment temperature). The width relaxation rate is preferably 1 to 10%. If it is less than 1%, the effect is small, and if it exceeds 10%, the flatness of the film deteriorates or the film becomes flaky in the tenter.

Here, a description has been given of a method of stretching in the width direction after the stretching in the longitudinal direction for the first time, but the stretching order may be reversed. In longitudinal stretching and transverse stretching, the stretching in each direction may be performed in one step, or in two or more steps. Further, as described above, in addition to the method of biaxially stretching the non-stretched film sequentially, it is also possible to adopt a biaxial stretching method in which the unoriented film is simultaneously stretched in the longitudinal direction and the transverse direction. However, in order to satisfy the characteristics of the present invention, it is important to take an optimal temperature condition, longitudinal and lateral stretch magnification, and the finally obtained film characteristics satisfy the requirements of the present invention.

Next, in the present invention, an example of a particularly preferable production method for obtaining a polyamide-based laminated biaxially stretched film satisfying the requirements of (Δnab), (4) and (5) in the claims is described.

Usually, the heat-setting treatment of the film after stretching is often carried out in a heat-fixing apparatus in which a plurality of plenum ducts having long hot-air blowing outlets are vertically arranged in the longitudinal direction. In the heat fixing device provided with such a plenum duct, the air in the heat fixing device is sucked by the circulating fan attached to the heat fixing device to adjust the temperature of the sucked air in order to improve the heating efficiency , And the hot air is circulated again by "taking out hot air → suctioning by a circulating fan → adjusting the temperature of the sucked air → taking out hot air" again by discharging it from the hot air blow-out port of the plenum duct again.

As described above, the difference between the HS160 of the difference in heat shrinkage ratio (one edge) and the HS160 of the other edge) in the width direction of the film is increased at the end edge in the width direction of the film, It can not be done. As shown in Fig. 1, there is a method of covering large-sized shielding plates S, S ... continuing to the central portions of the hot air blow-out ports 2, 2 ... of the respective plenum ducts 3, (See Japanese Patent Application Laid-Open No. 2001-138462), in the case of a short film, the heat-fixing treatment in the post-processing is carried out at a low temperature, but the passing property is improved. However, The heat-fixing treatment in the post-processing at a high temperature is not improved any more.

The inventors of the present invention have found that when a continuous large-size shielding plate is attached to the hot air blow-out port of the plenum duct, the inventors of the present invention have found that the "passing property in a long film" Passing property " was not improved, the analysis of the phenomenon in the heat fixing device was performed in detail. As a result, when a continuous large shielding plate that spans a plurality of plenum ducts is placed on the hot air blow-out port of the plenum duct, the flow of hot air blown out from the hot air blow-out port of the plenum duct by the shielding plate is significantly restricted, It is confirmed that the temperature hunting phenomenon occurs in the heat fixing apparatus due to the fact that the " circulation of the hot air " is not performed smoothly.

The inventors of the present invention have found that the above-described " hunting phenomenon of temperature " causes insufficient thermal relaxation at the edge of the film, and the "passability in a long film" ≪ / RTI > in the case of performing the heat treatment at a high temperature " Further, the inventors of the present invention have found that the above-described "circulation of hot air" is improved by adjusting the conditions of the temperature and air volume of the heat fixing device, and then improving the coating method when the hot air blowout port of the plenum duct is covered with the shielding plate The hunting phenomenon of the temperature can be suppressed, and further, the "passing property in the long film" and the "passing property in the case of performing the heat fixing treatment in the post-processing at a high temperature I think it can be improved. As a result of trial and error in order to grasp the relationship among the three factors of the temperature of the heat fixing device, the air flow rate condition, the coating method of the shielding plate, and the passing property of the film in the post-processing, It was found that the "passing property in a long film" and the "passing property in a case where heat setting treatment in a post-processing was performed at a high temperature" tended to be improved. As a result of further trial and error on the basis of the knowledge of the inventors, the inventors of the present invention have found out the means of (A) as a result of the trial and error and then take the means of (B) It has become possible to obtain a film having good transparency.

(A) Adjustment of the temperature and air volume of the plenum duct in the heat fixing device

(B) Adjustment of the shutoff condition of the hot air blowout port of the plenum duct in the heat fixing device

(C) Blocking of heating between the stretching zone and the heat fixing device

Hereinafter, each of the above means will be described in order.

(A) Adjustment of the temperature and air volume of the plenum duct in the heat fixing device

In the production of the film of the present invention, it is preferable that the temperature difference between the adjacent heat fixing zones of the heat fixing device is set to be 250 占 폚 · m / s or less so that the hot air taken out from each plenum duct It is desirable to adjust the temperature and air volume. For example, in a case where the open and closed values are divided into the first to third heat fixing zones, the product of the temperature difference and the wind speed difference between the first zone and the second zone, And the product of the temperature difference and the wind speed difference of 250 占 폚 · m / s or less. As described above, when the discontinuous shield plate is attached to the hot air blow-out port of the plenum duct by adjusting the temperature and air volume of the hot air blown out from the hot air blow-out port of the plenum duct in each heat fixing zone, The circulation of the hot air in the fixing device is smoothly performed and the " hunting phenomenon of temperature " is effectively suppressed. Therefore, only the long heat-sealing process in the post- Can be obtained.

Further, when the product of the temperature difference and the wind speed difference between the adjacent heat fixing zones is set to 250 占 폚 占 m / s (for example, the temperature difference between adjacent heat fixing zones is set to 30 占 폚, Quot; hot air circulation " in the heat fixing apparatus is not performed smoothly, and the " temperature hunting phenomenon " can be effectively suppressed It is not preferable. In addition, when the product of the temperature difference between the adjacent heat fixing zones and the wind speed difference exceeds 250 占 폚 · m / s, the downstream fixed heat fixing zone in the upstream heat fixing zone The temperature difference of the air flowing into the zone becomes large and adversely affects the stability of the temperature in the width direction of the downstream heat-fixing zone, which is not preferable. The product of the temperature difference and the wind speed difference is preferably 200 占 폚 m / s or less, more preferably 150 占 폚 m / s or less.

(B) Adjustment of cut-off condition of plenum duct in the heat fixing device

In the production of the film of the present invention, as described above, the temperature and the air flow rate of the hot air taken out from the hot air blowout port of the plenum duct in each heat fixing zone are adjusted, and then the temperature of the hot air blown out to the plurality of plenum ducts Shaped shielding plates S and S to shield hot air blow-out ports (nozzles) 2, 2 ... of the respective plenum ducts 3, 3 ... one by one, as shown in Fig. 2, instead of mounting a large shielding plate . When the rod-like shielding plate is mounted on each plenum duct, the same length of the shielding plate is not attached to each plenum duct, but the length of the shielding plate It is preferable to gradually increase the length (see Fig. 1). The material of the shielding plate is preferably the same as that of the plenum duct in consideration of the thermal expansion in the heat fixing device, but it can withstand the temperature of the heat fixing device, Is not particularly limited as long as it does not adhere to the surface.

(C) Blocking of heating between the stretching zone and the heat fixing device (installation of the intermediate zone)

The biaxially stretched polyamide based resin film is usually produced by thermally fixing treatment after longitudinally or transversely stretched as described above. In the production of the film of the present invention, however, the longitudinally and transversely stretched zones and the heat- It is preferable to provide an intermediate zone between the fixing apparatuses in which positive blowing of hot air is not carried out to completely block the heating between the stretching zone and the heat fixing apparatus. More specifically, when a rectangular piece (paper piece) is applied between the stretching zone and the heat fixing device in such a state that the stretching zone and the hot pressing property are adjusted under the same conditions as in the production of the film, It is preferable to block the hot air in the drawing zone and the heat fixing device so as to be drained downward in the vertical direction. Further, the intermediate zone in which the positive hot air is not blown like this may be surrounded by the housing, or may be provided so as to expose a continuously produced film. If the interruption of the hot air in the intermediate zone is insufficient, the shielding effect by the shielding plate in the heat fixing apparatus becomes insufficient, and the good film passability at the time of post-processing can not be obtained.

As described above, by employing the above-described methods (A) to (C), the "circulation of hot air" in the heat fixing apparatus can be smoothly performed and the "hunting phenomenon of temperature" As a result, it is possible to sufficiently promote the relaxation in the longitudinal direction at the end edge in the width direction. As a result, the "passing property in a long film" or the "passing property in a case where heat- Can be improved. In the above description, a method of suppressing the "temperature hunting phenomenon" by smoothly executing the "circulation of the hot air" in the heat fixing device provided with the plenum duct is shown. The above description discloses a technical idea of how the film of the present invention can be obtained by applying heat energy to a film at a production level. However, those skilled in the art can easily carry out such a technical idea in a different manner from the above- The films of the present invention can be obtained in different ways. That is, even in the case of other types of heat fixing devices, by imparting to the film sufficient heat energy to smoothly perform "circulation of hot air" to suppress "hunting phenomenon of temperature" and then sufficiently relax in the longitudinal direction at the end edge in the width direction , It is possible to obtain a film improved in the "passing property in a long film" and the "passing property in a case where the heat setting treatment in the post-processing is performed at a high temperature" as in the film of the present invention.

In order to obtain a film having particularly small thickness unevenness in the polyamide based laminated film of the present invention, in the melt-extrusion step of the resin, the sheet of the molten resin extruded from the T die into a flat plate is cooled on a cooling roll to produce an unstretched polyamide It is preferable to use a method of increasing the adhesion between the molten resin sheet and the cooling roll by forming a corona discharge in the streamer corona state between the electrode and the melt extruded polyamide based resin sheet. This makes it possible to obtain an unoriented sheet of a polyamide-based resin having a stable characteristic and a thickness because a current of tens of times or more can be applied compared with the above-described electrostatic-application-molding method. Here, the corona discharge in the streamer corona state refers to a stable corona state in which an electrode and an earth plate (molten resin sheet) are bridged (see Japanese Patent Application Laid-Open No. 62-41095). When the electrode is in the positive potential, a corona concentrated in the form of a bar is formed on the molten sheet from the tip of the electrode. In the case of the negative potential, a corona spreading from the current front end to the molten sheet is formed. As the corona discharge in the streamer corona state, the corona discharge in either state can be employed.

In the present invention, in the case of obtaining an unstretched polyamide resin sheet using a corona discharge in a streamer corona state, it is preferable to dispose discharge points discontinuously in order to stably generate a corona discharge in the streamer corona state . For this purpose, for example, it is preferable to use a multi-needle electrode (an electrode in which a plurality of needle-like bodies are elongated from a long-axis support coated with an insulating material such as silicon in parallel in almost the same direction) or a sawtooth electrode. It does not. The number of discharge points and the arrangement method can be arbitrarily selected. In addition, the material of the whole room may be any material as long as it is electrically conductive, and examples thereof include metals (particularly, stainless steel) and carbon. It is preferable that the needle-shaped body of the multi-needle electrode has an acute angled tip. When the tip of the needle-like body has an acute angle, when the thickness of the portion other than the tip end is 0.5 to 5.0 mm (diameter), the streamer corona discharge state becomes more stable and is preferably 1.0 to 3.0 mm . In addition, it is not necessary to discharge the molten resin sheet from all the needle-shaped members of the multi-needle electrode, and it is possible to appropriately change the interval of the streamer corona discharge by adjusting the applied voltage or the like.

In order to stably generate the corona discharge in the streamer corona state in the method of the present invention, for example, the gap between the discharge point of the electrode and the molten resin sheet is preferably 2 to 20 mm, more preferably 2 to 10 mm Mm is particularly preferable. By arranging the discharge points as described above, a stable streamer corona discharge accompanied by brilliance is generated between the electrodes and the polyamide-based resin sheet in a molten state, and at the same time, high current flows. The thickness of the sheet to be formed in the present invention is not particularly limited, but is preferably 5 to 500 μm, more preferably 100 to 300 μm. On the other hand, the pulling speed of the sheet to be formed in the present invention is not particularly limited. The maximum speed at which the current can be drawn by the conventional electrostatic charge forming method is about 50 m / min. However, in the method of the present invention, it is possible to perform close-contact cooling even at a draw speed of about 80 m / min. In addition, as described above, when the streamer corona discharge is used, the maximum drawable speed is drastically increased. However, when a streamer corona discharge is used at a normal draw speed, the film forming property becomes more stable, Is significantly reduced.

In addition, as described above, when the streamer corona discharge is performed, adjusting the applied voltage in the range of 7 to 14 kv is preferable because variations in thickness in the longitudinal direction of the film roll, variations in physical properties and variations are reduced . Further, in the method for producing a film roll of the present invention, it is preferable that the deviation of the applied voltage be suppressed within an average voltage (set value) within ± 20%, and more preferably within ± 10%.

Furthermore, as described above, when the streamer corona discharge is performed, the atmosphere around the electrodes is maintained at a humidity of 40 to 85% RH and at a temperature of 35 to 55 DEG C, When the dew point is not formed, it is possible to prevent the oligomer (oligomer of? -Caprolactam, etc.) from adhering to the tip of the needle or the end of the saw blade of the electrode because the streamer corona discharge becomes stable. A more preferable range of humidity is 60 to 80% RH, and a more preferable temperature range is 40 to 50 캜.

Next, the method of the present invention will be described with reference to the drawings. Fig. 5 is an explanatory diagram showing one embodiment of a sheet manufacturing process of the method of the present invention. Fig. 5, the sheet-like molten body 12 is extruded from the die 11 and cooled and solidified by the cooling drum 13 to become an unstretched sheet 14. [ A voltage is applied to the electrode 16 by the DC high voltage power supply 15 and a streamer corona discharge 17 is generated from the electrode 16 to the sheet molten bath.

In order to obtain a film having a small thickness unevenness such as the polyamide laminated film of the present invention, in addition, when the melted resin is wound around a cooling roll such as a metal roll, the air gap (that is, And a portion contacting the surface of the cooling roll with a suction device such as a buzzing box (buzzing chamber) having a wide suction port is used for melting It is preferable to use a method in which the molten resin is forcibly brought into close contact with the metal roll by suctioning the resin in the direction opposite to the winding direction over the entire width of the resin. At this time, the suction wind speed of the suction portion is preferably adjusted to 2.0 to 7.0 m / sec, more preferably 2.5 to 5.5 m / sec. In order to facilitate the adjustment of the suction air velocity in the suction port, the suction port is divided into a predetermined number of sections in the lateral direction, so that each section It is preferable that the adjustment of the suction air velocity is made possible. In addition, when the casting speed is increased, accompanying flow accompanies the rotation of the metal roll, and adhesion of the molten resin to the metal roll is hindered. Therefore, the suction by the suction device is made more effective, A shield plate widely formed of a soft material such as Teflon (registered trademark) is provided on the upstream side (opposite to the rotating direction of the metal roll with respect to the suction device) adjacent to the suction device in order to improve the degree of close contact with the roll , It is preferable to shut off the accompanying flow. In addition, it is preferable to suppress the deviation of the suction wind speed of the buzzing box within the average suction wind speed (set value) ± 20%, more preferably, within ± 10%. In addition, it is desirable to provide a filter in the bag box so as to prevent the suction air velocity of the bag box from fluctuating by dust of the oligomer, and to adjust the suction force by feeding back the differential pressure before and after the filter.

The polyamide laminated biaxially stretched film of the present invention may contain various additives such as a lubricant, an antiblocking agent, a heat stabilizer, an antioxidant, an antistatic agent, an anti-light agent, and an impact resistance improver within a range that does not impair characteristics It is also possible. In particular, for the purpose of improving the activity of the biaxially stretched film, it is preferable to contain various inorganic particles. Addition of an organic lubricant such as ethylenebisstearic acid, which exhibits an effect of lowering the surface energy, is preferable because the activity of the film constituting the film roll becomes excellent.

The polyamide laminated biaxially stretched film of the present invention may be subjected to a heat treatment or a humidity control treatment in order to improve the dimensional stability depending on the application. Further, in order to improve the adhesiveness of the film surface, it is possible to perform corona treatment, coating treatment, fire treatment or the like, or to perform printing, vapor deposition or the like.

Hereinafter, as a preferred embodiment of the present invention, a method of applying an adhesive modifying resin to the surface of a polyamide-based laminated biaxially stretched film will be described. In the present invention, the term "dispersion" refers to an emulsion, dispersion or suspension, and "grafting" refers to introducing a graft portion of a polymer different from the main chain into the polymer main chain. Ester "refers to a polyester having a graft moiety made of a polymer different from the polyester with respect to the polyester main chain, and the term" aqueous solvent "refers to a solvent mainly containing water and optionally containing an aqueous organic solvent.

(Copolymerized polyester aqueous dispersion)

The copolymer polyester aqueous dispersion for use in the present invention contains particles of grafted polyester and water, an aqueous solvent or an organic solvent, and exhibits a translucent to milky white appearance. The grafted polyester preferably has a graft portion formed by a radically polymerizable monomer including a polyester main chain and a radically polymerizable monomer having a hydrophilic group.

The average particle size of the grafted polyester particles in the copolymer polyester aqueous dispersion measured by the laser light scattering method is preferably 500 nm or less, more preferably 10 nm to 500 nm, and still more preferably 10 nm to 300 nm to be. When the average particle size exceeds 500 nm, the coating film strength after coating is lowered.

The content of the grafted polyester particles in the copolymer polyester aqueous dispersion is preferably 1% by weight to 5% by weight, and more preferably 3% by weight to 30% by weight.

When the 13C-NMR (measurement conditions: 125 MHz, 25 DEG C, measuring solvent; heavy water, and the signal of DSS is 5 Hz or less) of the copolymer polyester aqueous dispersion which can be used in the present invention, , The half width of the signal of the carbonyl carbon derived from the main chain of the polyester is preferably 300 Hz or more and the half width of the signal of the carbonyl carbon originating in the graft portion is preferably 150 Hz or less .

Generally, it is known that the chemical shift, the half-width and the relaxation time in 13 C-NMR can be changed by reflecting the surrounding environment in which the carbon atom to be observed is placed. For example, the signal of the carbonyl carbon of the polymer dissolved in the heavy water is observed in the range of 170 to 200 ppm, and its half width is about 300 Hz or less. On the other hand, the signal of the carbonyl carbon of the polymer insoluble in heavy water is observed in the range of 170 to 200 ppm, and its half width is about 300 Hz or more.

By having the polyester main chain and the graft portion in the grafted polyester particles have the half-width as described above, the particles in the copolymer polyester aqueous dispersion which can be used in the present invention can be obtained by dispersing the core - Can take a shell structure.

The core-shell structure referred to herein is a core-shell structure, as is well known in the art, in which a core portion of a polymer that is in an aggregated state insoluble in a dispersion medium is poured into a shell portion of a polymer that is soluble in the dispersion medium Two-layer structure. This structure is a structure in which a polymer having a different solubility in a dispersion medium is chemically bonded to each other and is characterized in a dispersion of a complex polymer. The structure is not simply expressed by merely mixing a polymer having a different solubility in a dispersion medium . Further, a mixture of polymers having different solubilities in a simple dispersion medium can not exist as a dispersion having a particle diameter of 500 nm or less.

Since the particles in the copolymer polyester aqueous dispersion which can be used in the present invention have the above-described core-shell structure, it is possible to disperse the polymer particles into the dispersion medium of the polymer particles without using an emulsifier or an organic co- The dispersion state is stabilized. This is because the resin in the shell portion forms a sufficient hydration layer to protect the dispersed polymer particles.

The coating film obtained from such a co-polyester aqueous dispersion is excellent in adhesion to a polyamide film. In addition, since the blocking resistance is very excellent, it can be used without problems even in a film substrate having a comparatively low glass transition point. Further, in the case of using a laminate, adhesion to printing ink and an adhesive used for lamination of the sealant layer is also excellent. Therefore, by using the polyamide based resin laminated film of the present invention, the resulting laminate (laminate film) can remarkably improve durability in retort treatment and non-aqueous treatment. When the grafted polyester in the copolymer polyester aqueous dispersion has a glass transition temperature of 30 占 폚 or lower, preferably 10 占 폚 or lower, the durability of the laminate is further improved.

(Polyester main chain)

The polyester usable as the main chain of the grafted polyester in the present invention is preferably a saturated or unsaturated polyester synthesized with at least a dicarboxylic acid component and a diol component and the resulting polyester is one polymer or 2 It may be a mixture of more than two kinds of polymers. In addition, a polyester which is inherently not dispersed or dissolved in water is preferable. The weight average molecular weight of the polyester usable in the present invention is 5,000 to 100,000, preferably 5,000 to 50,000. If the weight average molecular weight is less than 5,000, physical properties such as post-processability of the dried coating film deteriorate. If the weight-average molecular weight is less than 5,000, the grafted polyester to be formed can not form a core-shell structure to be described later, because the polyester as a main chain is easily water-soluble. When the weight average molecular weight of the polyester exceeds 100,000, it becomes difficult to oxidize water. From the viewpoint of moisture oxidation, 100,000 or less is preferable.

The glass transition point is 30 占 폚 or lower, preferably 10 占 폚 or lower.

As the dicarboxylic acid component, at least one aromatic dicarboxylic acid, at least one aliphatic and / or alicyclic dicarboxylic acid, and at least one dicarboxylic acid having a radically polymerizable unsaturated double bond Is a dicarboxylic acid mixture. The aromatic dicarboxylic acid contained in the dicarboxylic acid mixture is 30 to 99.5 mol%, preferably 40 to 99.5 mol%, and the aliphatic and / or alicyclic dicarboxylic acid is 0 to 70 mol%, preferably 0 To 60 mol%, and the dicarboxylic acid having a radically polymerizable unsaturated double bond is 0.5 to 10 mol%, preferably 2 to 7 mol%, more preferably 3 to 6 mol%. When the content of the dicarboxylic acid containing a radically polymerizable unsaturated double bond is less than 0.5 mol%, it is difficult to effect effective grafting of the radically polymerizable monomer to the polyester, and the dispersion particle size in the aqueous medium tends to become large, The dispersion stability tends to be lowered.

As the aromatic dicarboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalene dicarboxylic acid, biphenyldicarboxylic acid and the like can be used. In addition, if desired, sodium 5-sulfoisophthalate may also be used.

As the aliphatic dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecadionic acid, dimeric acid, acid anhydrides thereof and the like can be used.

Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, and acid anhydrides thereof .

Examples of the dicarboxylic acid having a radically polymerizable unsaturated double bond include fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, and alicyclic dicarboxylic acids containing an unsaturated double bond as?,? -Unsaturated dicarboxylic acids 2,5-norbornenedicarboxylic acid anhydride, tetrahydrophthalic anhydride and the like can be used as the carboxylic acid. Of these, fumaric acid, maleic acid and 2,5-norbornene dicarboxylic acid (endo-bicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic acid) are preferred.

The diol component is at least one of an aliphatic glycol having 2 to 10 carbon atoms, an alicyclic glycol having 6 to 12 carbon atoms, and an ether bond-containing glycol.

Examples of the aliphatic glycol having 2 to 10 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butylpropanediol and the like.

As the alicyclic glycol having 6 to 12 carbon atoms, 1,4-cyclohexanedimethanol and the like can be used.

Examples of the ether bond-containing glycol include glycols obtained by adding one to several moles of ethylene oxide or propylene oxide to two phenolic hydroxyl groups of diethylene glycol, triethylene glycol, dipropylene glycol, and further bisphenols, for example, 2-bis (4-hydroxyethoxyphenyl) propane and the like can be used. Polyethylene glycol, polypropylene glycol, and polytetramethylene glycol may also be used as needed.

In addition to the dicarboxylic acid component and the diol component, polycarboxylic acids and / or polyols having three or more functionalities may be copolymerized.

Examples of the polycarboxylic acid having three or more functional groups include trimellitic acid, (anhydrous) pyromellitic acid, (anhydrous) benzophenonetetracarboxylic acid, trimesic acid, ethylene glycol bis (anhydrotrimellitate), glycerol tris (Anhydrotrimellitate) and the like can be used.

As the trifunctional or higher polyol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like can be used.

The polycarboxylic acid and / or polyol having three or more functional groups is preferably used in an amount of 0 to 5 mol%, preferably 0 to 5 mol%, based on the total polycarboxylic acid component containing the dicarboxylic acid component or the entire polyol component containing the diol component To 3 mol%.

(Graft portion of grafted polyester)

The grafted portion of the grafted polyester which can be used in the present invention may be a polymer derived from a monomer mixture having at least one radically polymerizable monomer having a hydrophilic group or a group capable of being changed into a hydrophilic group later.

The polymer constituting the graft portion has a weight average molecular weight of 500 to 50,000, preferably 4,000 to 50,000. When the weight-average molecular weight is less than 500, the grafting ratio is lowered, so that the impartation of hydrophilicity to the polyester is not sufficiently performed, and it is generally difficult to control the weight average molecular weight of the graft portion to less than 500. The graft portion forms the hydration layer of the dispersed particles. In order to obtain a hydrated layer having a sufficient thickness for the particles and to obtain a stable dispersion, the weight average molecular weight of the graft portion derived from the radical polymerizable monomer is preferably 500 or more. The upper limit of the weight average molecular weight of the graft portion of the radically polymerizable monomer is preferably 50,000 as described above in terms of polymerizability in solution polymerization. The adjustment of the molecular weight within this range can be performed by appropriately selecting the amount of the polymerization initiator, the dropping time of the monomer, the polymerization time, the reaction solvent, and the monomer composition, and appropriately combining a chain transfer agent and a polymerization inhibitor, if necessary.

The glass transition point is 30 占 폚 or lower, preferably 10 占 폚 or lower.

As the hydrophilic group of the radical polymerizable monomer, a carboxyl group, a hydroxyl group, a sulfonic acid group, an amide group, a quaternary ammonium salt, a phosphoric acid group and the like can be used. As the group capable of being converted into a hydrophilic group, acid anhydride, glycidyl, chlorine and the like can be used. The dispersibility of the grafted polyester into water can be controlled by the hydrophilic group introduced into the polyester by grafting. Among the hydrophilic groups, the carboxyl group is preferable for controlling the dispersibility of the grafted polyester into water, because the amount of the carboxyl group introduced into the grafted polyester can be accurately determined using an acid value known in the art.

Examples of the carboxyl group-containing radical polymerizable monomer include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid and the like. Further, maleic acid anhydride which easily generates carboxylic acid in contact with water / amine, itaconic anhydride , Methacrylic anhydride, and the like can be used. Preferred carboxyl-containing radically polymerizable monomers are acrylic acid anhydride, methacrylic acid anhydride, and maleic anhydride.

In addition to the hydrophilic group-containing radically polymerizable monomer, it is preferable to copolymerize at least one radically polymerizable monomer containing no hydrophilic group. In the case of only the hydrophilic group-containing monomer, grafting to the polyester main chain does not occur smoothly, and it is difficult to obtain a good copolymerized polyester aqueous dispersion. By copolymerizing at least one radically polymerizable monomer containing no hydrophilic group, grafting with high efficiency can be performed.

As the radically polymerizable monomer which does not contain a hydrophilic group, one or a combination of monomers having an ethylenic unsaturated bond and containing no such hydrophilic group is used. Examples of such monomers include acrylic acid esters such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate and hydroxypropyl acrylate; Methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, lauryl methacrylate, 2-hydroxyethyl methacrylate, Methacrylic acid esters such as hydroxypropyl methacrylate; Acrylic acid or methacrylic acid derivatives such as acrylamide, N-methylol acrylamide and diacetone acrylamide; Nitriles such as acrylonitrile and methacrylonitrile; Vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole and N-vinylpyrrolidone; Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride; And aromatic vinyl compounds such as styrene,? -Methylstyrene, t-butylstyrene, vinyltoluene, vinylnaphthalene and the like. These monomers may be used alone or in combination of two or more.

The ratio of the hydrophilic group-containing monomer to the monomer not containing a hydrophilic group is determined in consideration of the amount of the hydrophilic group to be introduced into the grafted polyester, but is usually in the range of 95: 5 (weight ratio: monomer containing no hydrophilic group: monomer containing no hydrophilic group) To 5:95, preferably from 90:10 to 10:90, and more preferably from 80:20 to 40:60.

When a carboxyl group-containing monomer is used as the hydrophilic group-containing monomer, the total acid value of the grafted polyester is 600-4,000 eq./106 g, preferably 700-3,000 eq./106 g, and most preferably 800-2,500 eq. / 106 g. When the acid value is 600 eq. / G or less, it is difficult to obtain a copolymerized polyester aqueous dispersion having a small particle diameter when the grafted polyester is dispersed in water, and the dispersion stability of the copolymerized polyester aqueous dispersion is deteriorated. When the acid value is 4,000 eq. / G or more, the water resistance of the adhesive modified film formed by the copolymer polyester aqueous dispersion becomes low.

The weight ratio (polyester: radical polymerizable monomer) of the polyester main chain to the graft portion in the grafted polyester is 40:60 to 95: 5, preferably 55:45 to 93: 7, more preferably 60: 40 to 90: 10.

When the weight ratio of the polyester main chain is 40% by weight or less, excellent performance of the matrix polyester described above, that is, high workability, excellent water resistance and excellent adhesion to various materials can not be sufficiently exhibited. On the other hand, That is, low workability, gloss, water resistance, and the like. When the weight ratio of the polyester is 95% by weight or more, the amount of the hydrophilic group in the graft portion imparting hydrophilicity to the grafted polyester is insufficient, and a good aqueous dispersion can not be obtained.

(Solvent for the grafting reaction)

The solvent of the grafting reaction is preferably composed of an aqueous organic solvent having a boiling point of 50 to 250 ° C. Here, the aqueous organic solvent means an organic solvent having a solubility in water at 20 캜 of at least 10 g / L or more, preferably 20 g / L or more. The aqueous organic solvent having a boiling point exceeding 250 캜 is not suitable because it can not be sufficiently removed by baking at a high temperature of the coating film after the formation of the coating film because the evaporation rate is slow. Further, in the case of an aqueous organic solvent having a boiling point of 50 캜 or less, when the grafting reaction is carried out using the solvent as a solvent, an initiator which decomposes into radicals at a temperature of 50 캜 or lower must be used, .

Examples of the water-soluble organic solvent (first group) that dissolve polyester well and dissolve the polymerizable monomer and the polymer thereof relatively easily include a hydrophilic group, particularly a carboxyl group-containing polymerizable monomer, include esters such as ethyl acetate; Ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Cyclic ethers such as tetrahydrofuran, dioxane, and 1,3-dioxolane; Glycol ethers such as ethylene glycol dimethyl ether, propylene glycol methyl ether, propylene glycol propyl ether, ethylene glycol ethyl ether, and ethylene glycol butyl ether; Carbitols such as methyl carbitol, ethyl carbitol, and butyl carbitol; Lower esters of glycols or glycol ethers, such as ethylene glycol diacetate and ethylene glycol ethyl ether acetate; Ketone alcohols such as diacetone alcohol; N-substituted amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

On the other hand, as the water-soluble organic solvent (second group) which relatively hardly dissolves the polyester but relatively easily dissolves the polymerizable monomer containing the hydrophilic group, particularly the carboxyl group-containing polymerizable monomer and the polymer thereof, water, lower alcohols, Glycols, lower carboxylic acids, lower amines and the like. Preferred are alcohols having 1 to 4 carbon atoms and glycols.

When the grafting reaction is carried out in a single solvent, one kind of the aqueous organic solvent of the first group can be used. In the case of conducting in a mixed solvent, it is possible to use a plurality of aqueous organic solvents of the first group or at least one of the aqueous organic solvents of the first group and at least one aqueous organic solvent of the second group.

The grafting reaction can be carried out either in a single solvent from the first group of aqueous organic solvents or in a mixed solvent of one of each of the first and second groups of aqueous organic solvents. However, from the viewpoints of the progressive behavior of the grafting reaction, the grafting reaction product and the appearance and properties of the aqueous dispersion derived therefrom, a mixed solvent consisting of one kind of each of the aqueous organic solvents of the first and second groups Is preferably used. This is because gelation of the system tends to occur due to crosslinking between the polyester molecules in the grafting reaction of the polyester, but gelation can be prevented by using a mixed solvent as described below.

Among the solvents of the first group, the polyester molecular chains are in a state in which the chain having a large spread is long. On the other hand, in the mixed solvent of the first group and the second group, the polyester molecular chains are thread- In the state of entanglement was confirmed by measuring the viscosity of the polyester in these solutions. In a state in which the polyester molecular chain is long, since all the reaction points in the polyester main chain can contribute to the grafting reaction, the grafting ratio of the polyester is high, and at the same time, the probability of cross-linking between molecules also increases. On the other hand, when the polyester molecular chain is in the form of a pore, the reaction point inside the hollow can not contribute to the grafting reaction, and the probability of cross-linking between molecules also lowers. Accordingly, the state of the polyester molecules can be controlled by selecting the kind of solvent, and thereby the grafting ratio and the intermolecular crosslinking due to the grafting reaction can be controlled.

Both the high grafting ratio and the gelling inhibition can be achieved in a mixed solvent system. The optimum mixing ratio of the mixed solvent of the first group / second group may be changed depending on the solubility of the polyester to be used, but usually the weight ratio of the mixed solvent of the first group / second group is 95: 10:90, preferably 90:10 to 20:80, and more preferably 85:15 to 30:70.

(Radical polymerization initiator and other additives)

As the radical polymerization initiator usable in the present invention, well-known organic peroxide products and organic azo compounds can be used in the art.

As organic peroxides, benzoyl peroxide, t-butyl peroxypivalate, and organic azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) And the like.

The amount of the radical polymerization initiator used for carrying out the grafting reaction is at least 0.2% by weight, preferably at least 0.5% by weight, based on the radical polymerizable monomer.

In addition to the polymerization initiator, a chain transfer agent for controlling the chain length of the graft moiety such as octyl mercaptan, mercaptoethanol, 3-t-butyl-4-hydroxyanisole and the like may be used as needed. In this case, it is preferably added in the range of 0 to 5% by weight relative to the radical polymerizable monomer.

(Grafting reaction)

The formation of the graft portion is carried out by the polymerization of the radically polymerizable unsaturated double bond in the polyester with the radically polymerizable monomer and / or by the reaction of the radically polymerizable unsaturated double bond with the active terminal of the polymer of the radically polymerizable monomer do. The reaction product after completion of the grafting reaction contains a grafted polyester other than the objective grafted polyester, and a polymer of a radically polymerizable monomer not grafted with polyester and polyester having no graft moiety. When the ratio of the grafted polyester in the reaction product is low, and the ratio of the polyester having no graft moiety and the polymer of the non-grafted radically polymerizable monomer is high, a dispersion having good stability can not be obtained.

Usually, the grafting reaction can be carried out by adding the radically polymerizable monomer and the radical initiator to the solution containing the polyester at a time under heating, or by dropwise taking a certain period of time separately, Followed by heating under stirring to continue the reaction. Alternatively, if necessary, a part of the radical polymerizable monomer is first added, and then the remaining radical polymerizable monomer and the polymerization initiator are separately added dropwise over a period of time, and further heating is continued under stirring for a predetermined time to perform grafting Can be performed.

The weight ratio of the polyester to the solvent is selected so that the reaction proceeds uniformly during the polymerization process in consideration of the reactivity of the polyester with the radically polymerizable monomer and the solvent solubility of the polyester. Is usually in the range of 70:30 to 10:90, preferably 50:50 to 15:85.

(Water oxidation of grafted polyester)

The grafted polyester which can be used in the present invention can be subjected to water oxidation by putting it in an aqueous medium in a solid state or after dissolving it in a hydrophilic solvent and putting it in an aqueous medium. Particularly, when a monomer having an acidic group such as a sulfonic acid group and a carboxyl group is used as the radically polymerizable monomer having a hydrophilic group, the grafted polyester can be easily neutralized with a basic compound to easily produce a grafted polyester with fine particles having an average particle size of 500 nm or less Dispersed in water to prepare a copolymer polyester aqueous dispersion.

As the basic compound, a compound which is volatilized at the time of forming a coating film or when the curing agent described below is blended, is preferably used. As such a basic compound, ammonia, organic amines and the like are preferable. Examples of the organic amines include triethylamine, N, N-diethylethanolamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl- But are not limited to, ethylamine, diethylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, dimethylaminopropylamine, Propylamine, monoethanolamine, diethanolamine, triethanolamine, and the like.

The amount of the basic compound to be used is preferably such that the pH value of the aqueous dispersion is adjusted to 5.0 to 9.0 by at least partial neutralization or complete neutralization of the carboxyl group contained in the graft portion.

As a method for preparing a co-polyester aqueous dispersion neutralized with a basic compound, after completion of the grafting reaction, the solvent is removed from the reaction solution under reduced pressure by using an extruder or the like to obtain a solution of the copolymerized polyester aqueous dispersion in the form of a melt phase or a solid phase By adding the aqueous basic compound solution to the basic compound aqueous solution and stirring with heating or by adding the basic compound aqueous solution to the reaction solution immediately after the completion of the grafting reaction and further continuing the heating and stirring (source port method) An aqueous dispersion can be prepared. In terms of convenience, the one-port method is preferable. In this case, if the boiling point of the solvent used in the grafting reaction is 100 DEG C or lower, part or all of the solvent can be easily removed by distillation.

(Application of Adhesion Modifying Resin)

In the polyamide film laminate of the present invention, a coating film is preferably formed by coating a polyamide film substrate with a coating agent comprising the above copolymerized polyester aqueous dispersion as an adhesive property modifying resin on at least one side of the polyamide film substrate .

The copolymer polyester aqueous dispersion can be used as a coating agent for forming an adhesive modifying coating in this state, but additionally a crosslinking agent (curing resin) is blended and cured to impart a high durability to the adhesive modifying coating can do.

Examples of the crosslinking agent include phenol formaldehyde resins of condensates of alkylated phenols, cresols and the like and formaldehyde; Amino resins such as adducts of urea, melamine, benzoguanamine and formaldehyde, and adducts thereof and alkyl ether compounds of alcohols having 1 to 6 carbon atoms; Polyfunctional epoxy compounds; Polyfunctional isocyanate compounds; Block isocyanate compounds; Multifunctional aziridine compounds; Oxazoline compounds and the like can be used.

Examples of the phenol formaldehyde resin include alkylated (methyl, ethyl, propyl, isopropyl or butyl) phenol, p-tert-amylphenol, 4,4'-sec-butyldiphenol, p- p-cresol, p-cyclohexylphenol, 4,4'-isopropylidene phenol, p-nonylphenol, p-octylphenol, 3-pentadecylphenol, phenol, phenyl o- and condensates of formaldehyde with phenols such as p-phenylphenol and xylenol.

As the amino resin, there may be mentioned, for example, methyl methoxyl ether, methoxylated methylol N, N-ethylene ether, methoxylated methylol dicyandiamide, methoxylated methylol melamine, methoxylated methylolbenzoguanamine, Melamine, butoxide methylolbenzoguanamine and the like. Of these, methoxylated methylol melamine, butoxymethylol melamine, and methylol benzoguanamine are exemplified.

Examples of the polyfunctional epoxy compound include diglycidyl ether of bisphenol A and oligomers thereof, diglycidyl ether of hydrogenated bisphenol A and oligomers thereof, diglycidyl orthophthalate, diglycidyl ester of isophthalic acid , Terephthalic acid diglycidyl ester, p-oxybenzoic diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester , Sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether and polyalkyl Trimethylolpropane triglycidyl ether, triglycidyl diglycidyl ether, trimellitic acid triglycidyl ester, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, diglycidyl Glycidyl propylene urea, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol triglycidyl ether, glycerol-alkylene oxide addition of water during triglycidyl ether and the like.

As the polyfunctional isocyanate compound, a low molecular weight or high molecular aromatic, aliphatic diisocyanate, or trivalent or higher polyisocyanate can be used. Examples of the polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, There is a trimer of an isocyanate compound. It is also possible to use an excess amount of the isocyanate compound and a low molecular active hydrogen compound such as ethylene glycol, propylene glycol, trimethylol propane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine and triethanolamine, , Polyether polyols, polyamides, and the like can be given as examples of the terminal isocyanate group-containing compound.

The blocked isocyanate can be prepared by subjecting the isocyanate compound and the blocking agent to an addition reaction in a conventionally known appropriate manner. Examples of the isocyanate blocking agent include phenols such as phenol, cresol, xylenol, resorcinol, nitrophenol and chlorophenol; Thiophenols such as thiophenol and methylthiophenol; Oximes such as acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime; Alcohols such as methanol, ethanol, propanol and butanol; Halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol; tertiary alcohols such as t-butanol and t-pentanol; lactams such as? -caprolactam,? -valerolactam,? -butyrolactam and? -propyllactam; Aromatic amines; Imide; Active methylene compounds such as acetylacetone, acetoacetic acid ester and malonic acid ethyl ester; Mercaptans; This mankind; Elements; Diaryl compounds; And sodium bisulfite.

These crosslinking agents may be used alone or in combination of two or more.

The blending amount of the crosslinking agent is preferably 5% by weight to 40% by weight with respect to the grafted polyester.

Examples of the method of mixing the crosslinking agent include (1) a method of dissolving or dispersing the crosslinking agent directly in the aqueous dispersion when the crosslinking agent is water soluble, or (2) a method of adding the crosslinking agent before or after the water- So that the core portion is allowed to coexist with the polyester. These methods can be appropriately selected depending on the type and properties of the cross-linking agent. In addition, a curing agent or an accelerator may be used in combination with the crosslinking agent.

Additives such as an antistatic agent, an inorganic lubricant, and an organic lubricant may be mixed with the coating agent usable in the present invention within the range not impairing the effect of the present invention.

In the present invention, additives such as an antistatic agent, an inorganic lubricant, and an organic lubricant may be added to the adhesive modifying resin during the application of the adhesive modifying resin, so long as the effect of the present invention is not impaired. .

As a method for applying a coating agent containing a copolymerized polyester aqueous dispersion to a polyamide film substrate to form an adhesive modified film, a known coating method such as a gravure method, a reverse method, a die method, a bar method, Can be used.

The coating amount of the coating agent is preferably 0.01 to 1 g / m 2, preferably 0.02 to 0.5 g / m 2 as solid content. When the coating amount is less than 0.01 g / m 2, it is difficult to obtain sufficient adhesion strength between the adhesive modifying coating film and other layers, which is not preferable. If it exceeds 1 g / m < 2 >, blocking occurs and there is a practical problem.

The application of the adhesive modifying resin can be carried out, for example, by applying a coating agent to a biaxially stretched polyamide film base material, or applying a coating agent to a polyamide film base material after unstretched or uniaxially stretched, drying, Followed by stretching or biaxial stretching, followed by heat fixation. The drying temperature after application of the coating agent is preferably at least 150 ° C, and more preferably at least 200 ° C, so that the coating film is strengthened to improve adhesion between the adhesive property modifying film and the polyamide film base.

In the case of stretching after application, it is preferable to control the moisture content of the application film in the range of 0.1 to 2% in order not to impair the stretchability of the application film after the application. After stretching, the film is strengthened by drying and heat setting at 200 ° C or higher, and the adhesion property between the adhesive property modifying film and the polyamide film base material is remarkably improved.

In the present invention, the application of the adhesive modifying resin is preferably carried out by applying a coating agent containing a copolymerized polyester aqueous dispersion, and the copolymerized polyester aqueous dispersion is prepared by coating the grafted polyester particles with an aqueous solvent , And the grafted polyester preferably has a graft portion formed by a radically polymerizable monomer including a polyester main chain and a radically polymerizable monomer having a hydrophilic group.

When the laminated film of the polyamide based resin laminated film of the present invention obtained as described above is used for lamination, for example, the following ink layer, adhesive layer and sealant layer can be provided.

(Ink layer)

In the polyamide-based film laminate of the present invention, the ink layer may be laminated on the adhesive-modified film formed on the polyamide film substrate.

As the printing ink for forming the ink layer, an ink using a cellulose derivative as a binder or a gravure ink using a synthetic resin as a binder can be mainly used. Particularly when water resistance is required, a curing agent may be added to the ink using vinyl chloride, polyester, polyether, polyol or the like having a hydroxyl group at the end of the polymer chain as a binder. The ink layer is formed on the adhesive modifying coating in whole or in part or in any pattern.

(Adhesive layer)

In the polyamide-based film laminate of the present invention, an adhesive layer is laminated on the ink layer. The thickness of the adhesive layer is usually 0.1 탆 to 10 탆.

As the adhesive forming the adhesive layer, when the sealant layer laminated on the adhesive layer is laminated by the extrusion laminate, an isocyanate adhesive is preferable. As the isocyanate-based adhesive, for example, a polyurethane or polyurethane prepolymer having an isocyanate group at the molecular terminal may be used as a one-component type, for example, as a reaction product of a diisocyanate and a polyhydric alcohol. Alternatively, a liquid type in which a polyisocyanate and a polyol or a polyurethane prepolymer having a hydroxyl group at the molecular end are mixed immediately before use can be used.

When the sealant layer laminated on the adhesive layer is laminated by dry lamination, a known vinyl-based, acrylic-based, polyamide-based, epoxy-based or urethane-based adhesive may be used for the adhesive. Among these, a liquid-type polyurethane-based adhesive in which a polyisocyanate and a polyol are mixed immediately before use is preferable.

The adhesive layer can be formed by applying the liquid adhesive onto the ink layer using a method known to a person skilled in the art.

(Sealant layer)

In the polyamide-based film laminate of the present invention, a sealant layer is laminated on the adhesive layer. The thickness of the sealant layer is usually 20 to 100 占 퐉. The sealant layer can be formed by extrusion laminating or dry laminating a synthetic resin such as low density polyethylene (LDPE), ethylene-vinyl acetate copolymer (EVA), ionomer, polypropylene (PP) The adhesive modifying coating is located on the outermost surface of at least one side of the polyamide based laminated biaxially stretched film of the present invention. It is preferable that the ink layer, the adhesive layer, and the sealant layer are disposed on the adhesive modifying coating.

It is also possible that an inorganic vapor-deposited film is formed on the polyamide-based film. This inorganic vapor-deposited film imparts a high gas barrier property to the resulting polyamide-based resin film. As the material of the inorganic deposit film having such an action, a metal or a nonmetal such as Al, Si, Ti, Zn, Zr, Mg, Ce, Sn, Cu, Fe, or an oxide, nitride, fluoride, sulfide Specific examples thereof include SiOx (x = 1.0 to 2.0), alumina, magnesia, zinc sulfide, titania, zirconia, cerium oxide, or a mixture thereof. The inorganic vapor deposition film may be a single layer or a laminate of two or more layers.

The film thickness of the inorganic vapor deposition film is preferably 5 to 500 nm, more preferably 5 to 200 nm. If the film thickness is less than 5 nm, sufficient gas barrier properties may not be obtained, which is not preferable. On the other hand, when the thickness is more than 500 nm, the effect equivalent thereto is not exhibited, and the bending resistance is lowered, and further, the production cost is disadvantageously deteriorated.

As the method for forming the inorganic vapor deposition film, a known method such as a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method and an ion plating method, a chemical vapor deposition method such as PECVD and the like are employed.

In the vacuum deposition method, a metal such as aluminum, silicon, titanium, magnesium, zirconium, cerium, zinc, or a nonmetal as an evaporation material, or a mixture of SiOx (x = 1.0 to 2.0), alumina, magnesia, zinc sulfide, titania, Compounds and mixtures thereof are used. As the heating method, resistance heating, induction heating, electron beam heating, and the like are employed. Alternatively, a reactive vapor deposition method using oxygen, nitrogen, hydrogen, argon, carbonic acid gas, water vapor, or the like as a reaction gas or using means such as ozone addition or ion assist may be employed. Further, a method of applying a bias to the polyamide-based film or heating and cooling the polyamide-based film may also be employed. The deposition material, the reactive gas, the bias application, and the heating and cooling can be employed also in the sputtering method and the CVD method. It is also possible to provide an anchor coat layer between the inorganic substance-deposited film and the polyamide-based resin film, if necessary.

The vapor-deposited polyamide based laminated resin film of the present invention may be formed on at least one side of a polyamide based laminated biaxially stretched film preferably used as a substrate, but a resin layer mainly composed of an aliphatic polyamide resin ) Side of the film.

It is preferable that the vapor-deposited polyamide laminated resin film of the present invention and the laminated film of the polyethylene film having a thickness of 40 탆 have an oxygen permeability of 50 ml / m 2 24 H 占 a a or less at a temperature of 23 占 폚 and a relative humidity of 65%.

Since the oxygen permeability falls within the above range, the vapor-deposited polyamide laminated resin film of the present invention effectively exhibits the effect of preventing the deterioration of the quality of the contents when the gas barrier packaging material using the same is stored for a long period of time . The oxygen permeability is more preferably 40 ml / m < 2 > .24H.multidot.MPa or less, and particularly preferably 30 ml / m < 2 >

A laminated film obtained by laminating the vapor-deposited polyamide-based laminated resin film of the present invention and a polyethylene film having a thickness of 40 탆 was laminated to a laminate film having a thickness of 1 占 퐉 by using a gelboplex tester in an atmosphere of a temperature of 23 占 폚 and a relative humidity of 50% It is preferable that the number of pinholes is 10 or less when a bending test of 2000 cycles is continuously performed at a speed of 40 cycles per minute. Of course, the most preferable number is zero.

A method of measuring the pinhole number is as follows. A film laminated with a polyolefin film or the like and cut to a predetermined size (20.3 cm x 27.9 cm) is conditioned under a predetermined temperature for a predetermined time, and then the rectangular test film is rolled into a cylindrical shape having a predetermined length. Then, both ends of the cylindrical film were fixed to the outer circumference of the disk-shaped fixing head of the gelboplex tester and the outer circumference of the disk-shaped movable head, respectively, and the movable head was moved in the direction of the fixed head, (4.40 cm) while approaching a predetermined length (7.6 cm) along the axes of both heads, and after advancing a predetermined length (6.4 cm) without continuing to rotate, their operation is performed in the reverse direction, The bending test of one cycle of returning to the initial position is continuously repeated for a predetermined cycle (2000 cycles) at a predetermined speed (40 cycles per minute). Then, the number of pinholes occurring in a predetermined range (497 cm 2) except the fixed head of the tested film and the portion fixed to the outer periphery of the movable head is measured.

Due to the fact that the number of pinholes is in the above range, the vapor-deposited polyamide laminated resin film of the present invention can not be easily peeled off due to pores or minute pores caused by vibration, impact, It is possible to effectively exhibit the effect of preventing leakage of contents or deterioration of quality. It is more preferable that the number of pinholes is 8 or less, and it is particularly preferable that the number of pinholes is 6 or less.

As means for reducing the number of pinholes of the deposited polyamide laminated resin film of the present invention to 10 or less, it is preferable that the resin layer (A layer) containing a methacryloxy group-containing polyamide polymer as a main component is made as thin as possible At the same time, it can be achieved by suitably containing a thermoplastic elastomer in a resin layer (layer B) mainly composed of an aliphatic polyamide resin.

As means for reducing the oxygen permeability of the laminated film of the vapor-deposited polyamide-based laminated resin film of the present invention and the polyethylene film of 40 탆 thick to 50 ml / m 2 · 24H · MPa or less, The proportion of the methacrylic group-containing polyamide polymer in the resin layer (A layer) composed mainly of the polyamide polymer is maximized and the ratio of the thickness of the A layer is appropriately adjusted within a range of 10 to 30% Thereby forming an inorganic vapor-deposited film.

When a resin having a relatively high gas barrier property such as a methacrylic group-containing polyamide polymer is mixed with another resin having relatively low gas barrier properties such as an aliphatic polyamide resin, two types of resins are dispersed and homogenized , And acts to inhibit the formation of an effective gas barrier structure. As the mixing ratio increases, and the degree of mixing and homogenization increases, the gas barrier property tends to decrease. In the case where the gas barrier resin single layer and the single layer of the other resin are laminated in a state in which they are not completely mixed, the laminated film has the best gas barrier property, but in the case of lamination of the molten resin, Minute fluctuations may occur at the interface of the resin layer, and the gas barrier property may be slightly lowered.

The mixing method and the kneading conditions are adjusted so that the different resins are not contained in the A layer mainly composed of the methacrylic group-containing polyamide polymer, the proportion of other resins is minimized, and the different resins at the time of melt extrusion are not mixed as much as possible And the like.

The object of the present invention is to provide a polyamide laminate film having excellent storage stability of the packaging material using a polyamide film and protection against shock, .

Further, the vapor-deposited polyamide laminated resin film of the present invention was laminated with a polyethylene film having a thickness of 40 占 퐉 in an atmosphere at a temperature of 23 占 폚 and a relative humidity of 50% using a gelboplex tester at 40 cycles per minute , The oxygen permeability at a temperature of 23 캜 and a relative humidity of 65% is preferably 100 ml / m 2 · MPa · day or less.

The deterioration of the gas barrier properties of the deposited polyamide based laminated resin film by the bending treatment is mainly caused by occurrence of pinholes due to bending fatigue and breakage of the inorganic vapor deposition film at bent portions. On the other hand, the above-mentioned anti-flexural fatigue property and plasticity of the deposited polyamide based laminated resin film prevent the occurrence of pinholes and the breakage of the inorganic vapor deposition film and also the barrier property of the resin, Lt; / RTI >

INDUSTRIAL APPLICABILITY The vapor-deposited polyamide laminated resin film of the present invention has excellent elastic restoring force under room temperature or low temperature environment, exhibits excellent impact resistance and flexural fatigue resistance, and is excellent in processing suitability such as printing and lamination, It is a laminated film suitable as a packaging material.

The thickness of the vapor-deposited polyamide laminated resin film of the present invention is not particularly limited, but when it is used as a packaging material, the thickness is preferably 8 to 50 탆, more preferably 10 to 30 탆 Here, the thickness of the deposited polyamide laminated resin film of the present invention means the total thickness of the film including the deposited film, but the thickness of the deposited film is much thinner than the thickness of the base film, There will be no.

When the laminated film is produced by laminating the vapor-deposited polyamide laminated resin film of the present invention with a film such as another polyolefin, it is preferable that at least another film is laminated on the surface on which the vapor-deposited film is formed.

Example

Next, the present invention will be described in more detail with reference to Examples (Experimental Examples), but the present invention is not limited to the following Examples. The film was evaluated by the following measurement method. First, a method of measuring the properties of a material constituting the adhesive modifying coating applied to a film will be described below. In the following description, merely parts and parts are expressed by weight in terms of mixing, composition and the like, and what is simply expressed in% represents weight%.

[Weight average molecular weight]

0.03 g of the polymer was dissolved in 10 ml of tetrahydrofuran and measured with a GPC-LALLS apparatus low angle light scattering photometer LS-8000 (Tetrahydrofuran solvent, reference: polystyrene).

[Graft efficiency of polyester]

The product obtained by the grafting reaction was analyzed by 1 H-NMR (220 MHx, measurement solvent CDC13 / DMSO-d6) of a proton derived from a double bond of a double bond-containing component in polyester by using UNITY 500 And the graft efficiency was calculated based on the change in the intensity of the signal using Equation 1 below.

Polyester graft efficiency = (1- (relative intensity of signal originating from double bond of double bond-containing component in grafted polyester / relative intensity of signal originating from double bond of double bond-containing component in raw polyester)) x 100 (%) ... One

The relative intensities were also calculated by comparison with the signal intensities of the internal internals as standard signals.

[Measurement of weight average molecular weight of graft portion]

The grafted polyester was subjected to refluxing in a KOH / water-methanol solution to hydrolyze the polyester. The decomposition product was subjected to extraction using THF under acidic conditions, and the graft portion was purified from the extract by reprecipitation with hexane. The molecular weight of the obtained polymer was measured using a GPC apparatus (manufactured by Shimadzu Corporation, tetrahydrofuran solvent, in terms of polystyrene), and the weight average molecular weight of the graft portion was calculated.

[Particle size of aqueous dispersion]

The aqueous dispersion was adjusted to a solid concentration of 0.1 wt% using only ion exchange water and the particle size was measured at 20 캜 using a laser light scattering particle size distribution analyzer Coulter model N4 (manufactured by Coulter).

[B-type viscosity of aqueous dispersion]

The viscosity of the aqueous dispersion was measured at 25 캜 using a rotational viscometer (EM type, manufactured by TOKYO KAGAKU CO., LTD.).

[Measurement of full-width half-width of 13C-NMR signal]

The aqueous dispersion was diluted with heavy water to a solid concentration of 20% by weight, and then DSS was added thereto to prepare a sample for measurement. 13C-NMR (125 MHz) of the sample was measured after setting the measurement conditions such that the signal of the DSS was 5 Hz or less at 25 DEG C using UNITY 500 (manufactured by Barien) And converted to free space. The half-width of the signal of the carbonyl carbon of the obtained polyester main chain and the signal of the carbonyl carbon of the graft portion were respectively measured.

[Glass Transition Point (Tg)]

The aqueous dispersion was applied to a glass plate and then dried at 170 캜 to obtain a polyester solid. This polyester solid (10 mg) was poured into a sample pan, and the Tg was measured by scanning with a differential scanning calorimeter at a rate of 10 ° C / min.

On the other hand, the film was evaluated by the following evaluation method.

[Relative Viscosity (RV)]

0.25 g of the sample was dissolved in 25 ml of 96% sulfuric acid, and 10 ml of this solution was used to measure the falling water number at 20 캜 in an Oswald viscosity tube, and the relative viscosity was calculated by the following equation.

RV = t / to

However, to: the number of drops of solvent, and t: the number of drops of sample solution.

[Nab]

The refractive index (na) in a direction forming an angle of 45 degrees with the winding direction of the wound film was measured using an Abbe's refractometer 4T type manufactured by Atago Co. After the film specimen was left in an atmosphere of 23 DEG C and 65% RH for 2 hours or more, , And a refractive index nb in a direction forming an angle of 135 degrees with respect to the winding direction of the wound film (i.e., a direction forming an angle of 90 degrees with the above-described direction of 45 degrees). Then, the absolute value of the difference between the two refractive indexes was calculated as? Nab. The absolute value of the difference between the two refractive indexes was taken as DELTA nab and calculated as DELTA nab = | na-nb |. Nab was measured with respect to both edge portions of the film roll, and the larger one was designated as? Nab of the present invention.

[Heat Shrinkage Ratio of Film]

The width direction is evenly divided into five parts at a position apart from the portion of the film including the above-mentioned? Nab in the width direction by at least 80 cm from the portion containing 0.003 to 0.013 inclusive, and the sample is cut at the center of the part. After 30 minutes of seasoning in an atmosphere of 100%, HS160, which is the heat shrinkage ratio in the film winding direction when heated at 160 占 폚 for 10 minutes in the longitudinal direction, is obtained. A sample of 20 mm in length and 250 mm in length cut out from the above was placed in a heating oven controlled at 160 캜 at 200 ㎜ intervals and taken out. The sample was taken out at 23 캜 in an atmosphere of 50% for 30 minutes After seasoning, heat shrinkage is measured for each film. The average heat shrinkage rate of the film was calculated as an average value of the heat shrinkage ratios of five sample samples in the width direction. The difference between the maximum value and the minimum value is defined as the heat shrinkage difference.

[Transparency of Film]

A heat treatment was performed on the slit nozzle in which the temperature was set at 160 DEG C and the tension in the furnace was set at 100 N and the value of DELTA nab was 0.003 or more and 0.013 or less by using a coater having an interval of 1,900 mm between two rolls . Then, in order to evaluate the flatness of the film, the film was passed through two horizontally arranged rolls having a roll gap of 2,000 mm under a tension of 98 N. [ An iron bar was placed at a central position between rolls having a roll gap of 2,000 mm so that the top surface of the iron bar was positioned 30 mm below the common tangential line of the horizontally arranged roll top surface, Was evaluated as "? &Quot; when the film did not come into contact with the film, and " x " These processes were carried out continuously, and it was visually confirmed whether or not the film contacted the iron bar.

[Evaluation of Wrinkles of Sealing Sealing Portion]

A urethane-based AC ("EL443" manufactured by Toyo Moton Co., Ltd.) was applied to a biaxially oriented polyamide resin film using a film having a roll length of about 1,000 m, and then a single test laminator apparatus An LDPE (low density polyethylene) film having a thickness of 15 占 퐉 was extruded at 315 占 폚 and an LLDPE (linear low density polyethylene) film having a thickness of 40 占 퐉 was continuously laminated thereon to obtain a polyamide resin / LDPE / Thereby obtaining a laminated film having a layered laminated structure. The laminated film rolled up as the laminated film was thermally sealed at 150 캜 at 150 캜 at both ends in the longitudinal direction while folding the laminated film in parallel in the lengthwise direction of the roll using a test sealer manufactured by West Machinery Co., 10 mm was intermittently heat sealed at intervals of 550 mm to obtain a semi-finished product having a width of 280 mm. This was cut in the longitudinal direction of the roll in such a manner that both edge portions were cut to have a sealing portion of 10 mm and then cut at the boundary between the sealing portions in a direction perpendicular thereto to form a three-way sealing pouch (sealing width: 10 mm). After the three-way sealing pouches were closed, 10 bags were continuously sampled from a distance of 2 m to observe the sealing portion in the longitudinal direction to evaluate whether or not the sealing portion had wrinkles.

◎: 10 bags without any wrinkles at all

○: 1 to 3 bags with some wrinkles checked

X: There are more than four bags with some wrinkles being recognized

××: There is more than one bag with clear wrinkles.

[Oxygen Permeability (Gas Barrier Property)] [

The film was subjected to oxygen substitution in an atmosphere of a humidity of 65% RH and a temperature of 25 占 폚 for 2 days, and then the film was measured with a water acidity permeability measuring apparatus (OX-TRAN2 / 20: manufactured by MOCOM) according to JIS-K- ).

[Longitudinal thickness unevenness]

The film produced in the examples was slit to a width of about 3 cm across the entire length in the thickness direction to prepare a slit film for measurement of thickness unevenness. Then, the average thickness, the maximum thickness, and the minimum thickness over the entire length of the longitudinal direction were determined using a thickness unevenness measuring apparatus (wide sensitivity sensitive electromagnetic micrometer K-313A) manufactured by Anritsu. By calculating the difference between the maximum thickness and the average thickness of the minimum thickness and the average thickness and calculating the ratio (%) to the average thickness of the difference between the maximum thickness and the minimum thickness, The variation of thickness was calculated.

(%) = (| Maximum thickness or minimum thickness-average thickness | / average thickness) 占 100

[Production of laminate film]

A polyethylene-based liquid type adhesive (TM590 / CAT56 = 13/2 (parts by weight), manufactured by Toyo Moton Co., Ltd.) was applied at a coating amount of 3 g / m 2 to each of the films prepared in each Experimental Example and then a linear low density polyethylene film : Toyo Boseki Co., Ltd., L6102) 40 탆 was dry-laminated and aged for 3 days under an environment of 40 캜 to obtain a laminated film.

[Pinhole property]

The laminated film was cut into a size of 20.3 cm (8 inches) x 27.9 cm (11 inches), and a rectangular test film (laminated film) after the cut was subjected to a heat treatment under the conditions of a temperature of 23 DEG C and a relative humidity of 50% Or more. Then, the rectangular test film is rolled into a cylindrical shape having a length of 20.32 cm (8 inches). One end of the cylindrical film was fixed to the outer periphery of a disk-shaped fixing head of a gelboplex tester (Rigaku Kogyo Co., Ltd., NO.901 type) (conforming to the standard of MIL-B-131C) Was fixed to the outer periphery of the disk-shaped movable head of the tester opposed to the fixed head at a distance of 17.8 cm (7 inches). The movable head was then rotated 440 degrees in the direction of the fixed head while approaching 3.5 inches along the axes of both parallel opposing heads and straightened to 6.4 cm (2.5 inches) without further rotation, A cycle of bending test in which the operation was performed in the reverse direction to return the movable head to the initial position was repeated 2000 times in succession at a rate of 40 cycles per minute. Then, the cylindrical test sample was removed from the head, and a 17.8 cm (7 inch) x 27.9 cm (11 inch (10 inch)) portion excluding the fixed head of the rectangular film cut out of the bonded portion and the portion fixed to the outer periphery of the movable head ) Was measured by the following method (i.e., the pinhole number per 497 cm 2 (77 square inches) was measured). The L-LDPE film side of the test film was placed on the filter paper (Advantech, No. 50) with the lower side, and the four corners were fixed with Cellotape (registered trademark). The ink (Pilot Ink (product number INK-350-Blue) diluted 5 times with pure water) was applied on a test film and spread on one surface with a rubber roller. After wiping out unnecessary ink, the test film was removed and the number of ink dots attached to the filter paper was measured.

[Oxygen Permeability after Bending Treatment (Gas Barrier Property)] (Measurement Method for Deposited Film)

The laminate film was subjected to the same bending treatment as in the preceding item for 50 cycles. The sample was cut out from the central portion of the film after the treatment and oxygen was substituted for 2 days in an atmosphere at a humidity of 65% RH and a temperature of 25 占 폚. (OX-TRAN 2/20 manufactured by MOCOM CORPORATION) in accordance with K-7126 (Method B).

[Thickness of the deposited film] (Measurement method for the deposited film)

Section sections of a film sample having a vapor-deposited film are prepared, observed with a transmission electron microscope (TEM), and photographed to measure the thickness of the vapor-deposited film.

[Peel strength]

The laminated film was cut into 15 mm width and 200 mm length to prepare a test piece. Using a "Tensilon UMT-II-500 type" manufactured by Toyo Baldwin Co., The peel strength was measured between the layers of the laminated biaxially stretched film layer and the L-LDPE film layer. The tensile speed was 10 cm / min and the peel strength was 180 degrees.

[Water peeling strength]

The laminated film was cut into 15 mm width and 200 mm length to prepare a test piece. Using a "Tensilon UMT-II-500 type" manufactured by Toyo Baldwin Co., And the peel strength between the resin film layer and the L-LDPE layer was measured. The tensile strength was 10 cm / min and the peel strength was 180 deg.

[Heat Strength of Water Separation]

The laminate film was immersed in hot water at 90 占 폚 for 30 minutes and allowed to stand at room temperature for about 30 seconds. Thereafter, the laminate film was cut into a width of 15 mm and a length of 200 mm to prepare test specimens "Tensilon UMT-II-500 The peel strength between the polyamide based resin film layer and the L-LDPE layer was measured under the conditions of a temperature of 23 캜 and a relative humidity of 65%. The tensile strength was 10 cm / min and the peel strength was 180 deg.

[Storage stability test]

(a) Production of packaging pouch

Using the above laminate film, a three-directional sealing pouch having a side length of 15 cm and a length of 19 cm was produced by overlapping the linear low density polyethylene film side on the inner side.

(b) Production of color developing solution (coloring solution)

7 parts by weight of agar and 0.04 part by weight of methylene blue were added to 2,000 parts by weight of water and dissolved in warm water at 95 캜. In addition, 1.2 parts by weight of hydrosulfite (Na ₂ S ₂ O ₄ ) was added and mixed under a nitrogen atmosphere to give a colorless solution.

(c) In a nitrogen atmosphere, 250 ml of the coloring solution prepared in (b) above was placed in the three-way sealing bag prepared in the above (a), and the upper part of the bag was sealed while removing the gas in the bag. Cm and a length of 15 cm.

(d) The obtained bag was allowed to stand at room temperature for 3 hours, agar was hardened, and stored at 40 DEG C and humidity of 90%. After 2 weeks, the color of the methylene blue agar solution in the bag was observed. The evaluation method is as follows, and if it is ◯ or more, it is determined that there is no practical problem.

◎: No discoloration

○: Very slight blue discoloration

?: Slightly discolored

×: blue discoloration

[Vibration durability test]

Shaking tests were carried out in the following manner using packaging pouches containing the methylene blue coloring liquid prepared in the above (a) to (d). 20 pieces per one corrugated cardboard box were put into the test box, and the test pieces were placed in a shaking test apparatus and shaken for 24 hours under the condition of 5 ㎝ in stroke width and 120 times / minute in the horizontal direction at 23 캜 Were added. Subsequently, the solution was stored under the conditions of 40 DEG C and a humidity of 90%, and the coloring state of the methylene blue agar solution in the bag after 3 days was observed. The evaluation method is as follows, and if it is ◯ or more, it is determined that there is no practical problem.

◎: No discoloration

○: Very slight blue discoloration

?: Slightly discolored

×: blue discoloration

However,

Using the packing pouch containing the methylene blue coloring liquid prepared in the above (a) to (d), the rupture resistance test was carried out by the following method. Under the conditions of 5 占 폚 and humidity of 40%, 20 bags of packaging pouches were made into a bundle, and dropped onto the steel floor at a height of 1 m. This treatment was carried out once, and the damage of the outer appearance of the bag after 20 repeated treatments was confirmed, and it was judged that the tearing or the leakage of the contents due to the puncture was caused. It was also judged that the methylene blue agar solution in the bag stored for 3 days under the conditions of 40 DEG C and 90% humidity was significantly colored even if no damage was observed on the appearance. The evaluation method is as follows, and if it is ◯ or more, it is determined that there is no practical problem.

○: Wave ratio less than 10%

?: Wavelength ratio of 10% or more and less than 20%

×: wave ratio greater than 20%

First, Experimental Examples 1 to 9 of the present invention will be described.

[Experimental Example 1]

An unoriented sheet having the following constitution was obtained by using a two-kind three-layer coextrusion T-die apparatus. The total thickness of the unstretched sheet was 190 占 퐉 and the thickness ratio of each layer to the total thickness was 40% / 20% / 40% in the case of the layers B / A / B, , The extrusion resin temperature of the A layer is 270 占 폚, and the extrusion resin temperature of the B layer is 260 占 폚. Composition constituting the A layer: Composition composed of polymethoxy silylene adipamide (manufactured by Mitsubishi Gas Chemical Co., Ltd., RV = 2.65) = 100% by weight. 95% by weight of a composition constituting the layer B: nylon 6 (RV = 2.8, manufactured by Toyo Boseki Co., Ltd.) as a thermoplastic elastomer, a polyamide block copolymer (nylon 12 / polytetramethylene glycol copolymer, Box 4033, RV = 2.0).

The obtained non-stretched sheet was stretched 3.3 times in the longitudinal direction at a stretching temperature of 85 占 폚 by a roll, and subsequently stretched 3.7 times in the transverse direction at a stretching speed of 120 占 폚 by a tenter. And further heat-set at a temperature of 215 캜, and subjected to a heat relaxation treatment of 5% to prepare a biaxially stretched film having a thickness of 15 탆. In addition, corona discharge treatment was performed on the surface of the B layer on the side of 40 占 퐉 of the linear low-density polyethylene film (L-LDPE film: L6102 made by Toyobo Co., Ltd.) and on the side subjected to the dry lamination. The oxygen permeability and pinhole number of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 1.

[Experimental Example 2]

A biaxially stretched film was obtained in the same manner as in Experimental Example 1 except that the description of Experimental Example 1 was changed as follows.

Composition constituting the B layer: a composition comprising 98% of nylon 6 and 2% by weight of a polyamide block copolymer.

The oxygen permeability and pinhole number of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 1.

[Experimental Example 3]

A biaxially stretched film was obtained in the same manner as in Experimental Example 1 except that the description of Experimental Example 1 was changed as follows.

Composition constituting the B layer: a composition comprising 99% by weight of nylon 6 and 1% by weight of a polyamide block copolymer.

The oxygen permeability and pinhole number of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 1.

[Experimental Example 4]

A biaxially stretched film was obtained in the same manner as in Experimental Example 1 except that the description of Experimental Example 1 was changed as follows.

Composition constituting the B layer: 98% by weight of nylon 6 and 2% by weight of polyamide block copolymer.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 41% / 18% / 41%.

The oxygen permeability and pinhole number of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 1.

[Experimental Example 5]

A biaxially stretched film was obtained in the same manner as in Experimental Example 1 except that the description of Experimental Example 1 was changed as follows.

Composition constituting the B layer: a composition comprising 97% by weight of nylon 6 and 3% by weight of a polyamide block copolymer.

The thickness ratio of each layer to the total thickness is B layer / A layer / B layer = 39% / 22% / 39%.

The oxygen permeability and pinhole number of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 1.

[Experimental Example 6]

A biaxially stretched film was obtained in the same manner as in Experimental Example 1 except that the description of Experimental Example 1 was changed as follows.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 43% / 14% / 43%.

The oxygen permeability and pinhole number of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 1.

[Experimental Example 7]

A biaxially stretched film was obtained in the same manner as in Experimental Example 1 except that the description of Experimental Example 1 was changed as follows.

Composition constituting the B layer: 98% by weight of nylon 6 and 2% by weight of polyamide block copolymer.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 36% / 28% / 36%.

The oxygen permeability and pinhole number of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 1.

[Experimental Example 8]

A biaxially stretched film was obtained in the same manner as in Experimental Example 1 except that the description of Experimental Example 1 was changed as follows.

Composition constituting the B layer: a composition comprising 99% by weight of nylon 6 and 1% by weight of a polyamide block copolymer.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 43% / 14% / 43%.

The oxygen permeability and pinhole number of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 1.

[Experimental Example 9]

A biaxially stretched film was obtained in the same manner as in Experimental Example 1 except that the description of Experimental Example 1 was changed as follows.

Composition constituting the B layer: a composition comprising 93% by weight of nylon 6 and 7% by weight of a polyamide block copolymer.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 36% / 28% / 36%.

The oxygen permeability and pinhole number of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 1.

The following Experimental Examples 10 to 18 are comparative experimental examples for Experimental Examples 1 to 9.

[Experimental Example 10]

A biaxially stretched film was obtained in the same manner as in Experimental Example 1 except that the description of Experimental Example 1 was changed as follows.

Composition constituting layer B: nylon 6 Composition of 100% by weight.

The oxygen permeability and pinhole number of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 1.

[Experimental Example 11]

A biaxially stretched film was obtained in the same manner as in Experimental Example 1 except that the description of Experimental Example 1 was changed as follows.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 30% / 40% / 30%.

The oxygen permeability and pinhole number of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 1.

[Experimental Example 12]

A biaxially stretched film was obtained in the same manner as in Experimental Example 1 except that the description of Experimental Example 1 was changed as follows.

Composition constituting Layer A: 80% by weight of polymethylacrylene adipamide and 20% by weight of nylon 6.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 20% / 60% / 20%.

The oxygen permeability and pinhole number of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 1.

[Experimental Example 14]

A biaxially stretched film was obtained in the same manner as in Experimental Example 1 except that the description of Experimental Example 1 was changed as follows.

Composition constituting Layer A: 80% by weight of polymethylacrylene adipamide and 20% by weight of nylon 6.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 30% / 40% / 30%.

The oxygen permeability and pinhole number of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 1.

[Experimental Example 15]

A biaxially stretched film was obtained in the same manner as in Experimental Example 1 except that the description of Experimental Example 1 was changed as follows.

Composition constituting layer A: Composition comprising 90% by weight of polymethoxy silylene adipamide and 10% by weight of polyamide block copolymer.

Composition constituting layer B: nylon 6 Composition of 100% by weight.

The oxygen permeability and pinhole number of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 1.

[Experimental Example 16]

A biaxially stretched film was obtained in the same manner as in Experimental Example 1 except that the description of Experimental Example 1 was changed as follows.

Composition constituting the A layer: a composition comprising 90% by weight of polymethylacrylene adipamide and 10% by weight of nylon 6.

Composition constituting the B layer: a composition comprising 93% by weight of nylon 6 and 7% by weight of a polyamide block copolymer.

The thickness ratio of each layer to the total thickness is B layer / A layer / B layer = 15% / 70% / 15%.

The oxygen permeability and pinhole number of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 1.

[Experimental Example 17]

A biaxially stretched film was obtained in the same manner as in Experimental Example 1 except that the description of Experimental Example 1 was changed as follows.

Composition constituting Layer A: 96% by weight of nylon 6 and 4% by weight of polyamide block copolymer.

Composition comprising B layer: 97% by weight of nylon 6 and 3% by weight of polymethoxy silylene adipamide.

The thickness ratio of each layer to the total thickness is B layer / A layer / B layer = 15% / 70% / 15%.

The oxygen permeability and pinhole number of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. Their results are shown in Table 1.

[Experimental Example 18]

A biaxially stretched film was obtained in the same manner as in Experimental Example 1 except that the description of Experimental Example 1 was changed as follows.

Composition constituting Layer A: 96% by weight of nylon 6 and 4% by weight of polyamide block copolymer.

Composition constituting the B layer: a composition comprising 90% by weight of polymethylacrylene adipamide and 10% by weight of nylon 6.

The thickness ratio of each layer to the total thickness is B layer / A layer / B layer = 15% / 70% / 15%.

The oxygen permeability and pinhole number of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 1.

Experimental Examples 19 to 30, in which the peel strength described in claims is 4.0 N / 15 mm, will be described for Experimental Examples 1 to 9 below.

[Experimental Example 19]

An unoriented sheet having the following constitution was obtained by using a two-kind three-layer coextrusion T-die apparatus. The total thickness of the unstretched sheet was 190 占 퐉 and the thickness ratio of each layer to the total thickness was 40% / 20% / 40% in the case of the layers B / A / B, , The extrusion resin temperature of the A layer is 270 占 폚, and the extrusion resin temperature of the B layer is 260 占 폚. Composition constituting the A layer: Composition composed of polymethoxy silylene adipamide (manufactured by Mitsubishi Gas Chemical Co., Ltd., RV = 2.65) = 100% by weight. 89% by weight of a composition constituting the B layer: nylon 6 (RV = 2.8, manufactured by Toyo Boseki K.K.) as a thermoplastic elastomer, a polyamide block copolymer (nylon 12 / polytetramethylene glycol copolymer, 5% by weight of polyvinylidene fluoride resin (trade name: Box 4033, RV = 2.0), and 6% by weight of polymethoxy silylene adipamide (manufactured by Mitsubishi Gas Chemical Company, RV = 2.65).

The obtained non-stretched sheet was stretched 3.3 times in the longitudinal direction at a stretching temperature of 85 占 폚 by a roll, and then stretched 3.7 times in the transverse direction at a stretching temperature of 120 占 폚 by a tenter. And further heat-set at a temperature of 215 캜, and subjected to a heat relaxation treatment of 5% to prepare a biaxially stretched film having a thickness of 15 탆. In addition, corona discharge treatment was performed on the surface of the B layer on the side of 40 占 퐉 of the linear low-density polyethylene film (L-LDPE film: L6102 made by Toyobo Co., Ltd.) and on the side subjected to the dry lamination. The oxygen permeability, pinhole number and peel strength of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. The results are shown in Table 2.

[Experimental Example 20]

A biaxially stretched film was obtained in the same manner as in Experimental Example 19 except that the description of Experimental Example 19 was changed as follows.

Composition constituting the layer B: a composition consisting of 95% by weight of nylon 6, 2% by weight of a polyamide block copolymer and 3% by weight of polymethoxy silylene adipamide.

The oxygen permeability, pinhole number and peel strength of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. The results are shown in Table 2.

[Experimental Example 21]

A biaxially stretched film was obtained in the same manner as in Experimental Example 19 except that the description of Experimental Example 19 was changed as follows.

Composition constituting the B layer: a composition comprising 97% by weight of nylon 6, 1% by weight of a polyamide block copolymer, and 2% by weight of polymethoxy silylene adipamide.

The oxygen permeability, pinhole number and peel strength of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. The results are shown in Table 2.

[Experimental Example 22]

A biaxially stretched film was obtained in the same manner as in Experimental Example 19 except that the description of Experimental Example 19 was changed as follows.

Composition constituting the layer B: a composition consisting of 95% by weight of nylon 6, 2% by weight of a polyamide block copolymer and 3% by weight of polymethoxy silylene adipamide.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 41% / 18% / 41%.

The oxygen permeability, pinhole number and peel strength of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. The results are shown in Table 2.

[Experimental Example 23]

A biaxially stretched film was obtained in the same manner as in Experimental Example 19 except that the description of Experimental Example 19 was changed as follows.

Composition comprising B layer: 92% by weight of nylon 6, 3% by weight of polyamide block copolymer and 5% by weight of polymethylacrylene adipamide.

The thickness ratio of each layer to the total thickness is B layer / A layer / B layer = 39% / 22% / 39%.

The oxygen permeability, pinhole number and peel strength of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. The results are shown in Table 2.

[Experimental Example 24]

A biaxially stretched film was obtained in the same manner as in Experimental Example 19 except that the description of Experimental Example 19 was changed as follows.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 43% / 14% / 43%.

The oxygen permeability, pinhole number and peel strength of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. The results are shown in Table 2.

[Experimental Example 25]

A biaxially stretched film was obtained in the same manner as in Experimental Example 19 except that the description of Experimental Example 19 was changed as follows.

Composition constituting the layer B: a composition consisting of 95% by weight of nylon 6, 2% by weight of a polyamide block copolymer and 3% by weight of polymethoxy silylene adipamide.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 36% / 28% / 36%.

The oxygen permeability, pinhole number and peel strength of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. The results are shown in Table 2.

[Experimental Example 26]

A biaxially stretched film was obtained in the same manner as in Experimental Example 19 except that the description of Experimental Example 19 was changed as follows.

Composition constituting the B layer: a composition comprising 97% by weight of nylon 6, 1% by weight of a polyamide block copolymer, and 2% by weight of polymethoxy silylene adipamide.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 43% / 14% / 43%.

The oxygen permeability, pinhole number and peel strength of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. The results are shown in Table 2.

[Experimental Example 27]

A biaxially stretched film was obtained in the same manner as in Experimental Example 19 except that the description of Experimental Example 19 was changed as follows.

Composition constituting the B layer: Composition composed of 83% by weight of nylon 6, 7% by weight of polyamide block copolymer and 10% by weight of polymethoxy silylene adipamide.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 36% / 28% / 36%.

The oxygen permeability, pinhole number and peel strength of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. The results are shown in Table 2.

[Experimental Example 28]

A biaxially stretched film was obtained in the same manner as in Experimental Example 19 except that the description of Experimental Example 19 was changed as follows.

Composition constituting the B layer: a composition consisting of 93% by weight of nylon 6, 5% by weight of a polyamide block copolymer and 2% by weight of polymethoxy silylene adipamide.

The oxygen permeability, pinhole number and peel strength of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. The results are shown in Table 2.

[Experimental Example 29]

A biaxially stretched film was obtained in the same manner as in Experimental Example 19 except that the description of Experimental Example 19 was changed as follows.

Composition comprising B layer: 84% by weight of nylon 6, 5% by weight of polyamide block copolymer and 11% by weight of polymethoxy silylene adipamide.

The oxygen permeability, pinhole number and peel strength of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. The results are shown in Table 2.

[Experimental Example 30]

A biaxially stretched film was obtained in the same manner as in Experimental Example 19 except that the description of Experimental Example 19 was changed as follows.

Composition constituting the B layer: a composition consisting of 98% by weight of nylon 6, 1% by weight of a polyamide block copolymer and 1% by weight of polymethoxy silylene adipamide.

The oxygen permeability, pinhole number and peel strength of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. The results are shown in Table 2.

The following Experimental Examples 31 to 42 are comparative experimental examples for Experimental Examples 19 to 30.

[Experimental Example 31]

A biaxially stretched film was obtained in the same manner as in Experimental Example 19 except that the description of Experimental Example 19 was changed as follows.

Composition constituting layer B: nylon 6 Composition of 100% by weight.

The oxygen permeability, pinhole number and peel strength of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. The results are shown in Table 2.

[Experimental Example 32]

A biaxially stretched film was obtained in the same manner as in Experimental Example 19 except that the description of Experimental Example 19 was changed as follows.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 30% / 40% / 30%.

The oxygen permeability, pinhole number and peel strength of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. The results are shown in Table 2.

[Experimental Example 33]

A biaxially stretched film was obtained in the same manner as in Experimental Example 19 except that the description of Experimental Example 19 was changed as follows.

Composition constituting Layer A: 80% by weight of polymethylacrylene adipamide and 20% by weight of nylon 6.

The oxygen permeability, pinhole number and peel strength of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. The results are shown in Table 2.

[Experimental Example 34]

A biaxially stretched film was obtained in the same manner as in Experimental Example 19 except that the description of Experimental Example 19 was changed as follows.

Composition constituting Layer A: 80% by weight of polymethylacrylene adipamide and 20% by weight of nylon 6.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 20% / 60% / 20%.

The oxygen permeability, pinhole number and peel strength of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. The results are shown in Table 2.

[Experimental Example 35]

A biaxially stretched film was obtained in the same manner as in Experimental Example 19 except that the description of Experimental Example 19 was changed as follows.

Composition constituting Layer A: 80% by weight of polymethylacrylene adipamide and 20% by weight of nylon 6.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 30% / 40% / 30%.

The oxygen permeability, pinhole number and peel strength of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. The results are shown in Table 2.

[Experimental Example 36]

A biaxially stretched film was obtained in the same manner as in Experimental Example 19 except that the description of Experimental Example 19 was changed as follows.

Composition constituting the B layer: a composition comprising 95% by weight of nylon 6 and 5% by weight of a polyamide block copolymer.

The oxygen permeability, pinhole number and peel strength of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. The results are shown in Table 2.

[Experimental Example 37]

A biaxially stretched film was obtained in the same manner as in Experimental Example 19 except that the description of Experimental Example 19 was changed as follows.

Composition constituting the B layer: a composition comprising 99% by weight of nylon 6 and 1% by weight of a polyamide block copolymer.

The oxygen permeability, pinhole number and peel strength of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. The results are shown in Table 2.

[Experimental Example 38]

A biaxially stretched film was obtained in the same manner as in Experimental Example 19 except that the description of Experimental Example 19 was changed as follows.

Composition comprising B layer: 95% by weight of nylon 6 and 5% by weight of polymethoxy silylene adipamide.

The oxygen permeability, pinhole number and peel strength of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. The results are shown in Table 2.

[Experimental Example 39]

A biaxially stretched film was obtained in the same manner as in Experimental Example 19 except that the description of Experimental Example 19 was changed as follows.

Composition constituting layer A: Composition comprising 90% by weight of polymethoxy silylene adipamide and 10% by weight of polyamide block copolymer.

Composition constituting layer B: nylon 6 Composition of 100% by weight.

The oxygen permeability, pinhole number and peel strength of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. The results are shown in Table 2.

[Experimental Example 40]

A biaxially stretched film was obtained in the same manner as in Experimental Example 19 except that the description of Experimental Example 19 was changed as follows.

Composition constituting the A layer: a composition comprising 90% by weight of polymethylacrylene adipamide and 10% by weight of nylon 6.

Composition constituting the B layer: a composition comprising 93% by weight of nylon 6 and 7% by weight of a polyamide block copolymer.

The thickness ratio of each layer to the total thickness is B layer / A layer / B layer = 15% / 70% / 15%.

The oxygen permeability and pinhole number of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 2.

[Experimental Example 41]

A biaxially stretched film was obtained in the same manner as in Experimental Example 19 except that the description of Experimental Example 19 was changed as follows.

Composition constituting Layer A: 96% by weight of nylon 6 and 4% by weight of polyamide block copolymer.

Composition comprising B layer: 97% by weight of nylon 6 and 3% by weight of polymethoxy silylene adipamide.

The thickness ratio of each layer to the total thickness is B layer / A layer / B layer = 15% / 70% / 15%.

The oxygen permeability and pinhole number of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 2.

[Experimental Example 42]

A biaxially stretched film was obtained in the same manner as in Experimental Example 19 except that the description of Experimental Example 19 was changed as follows.

Composition constituting Layer A: 96% by weight of nylon 6 and 4% by weight of polyamide block copolymer.

Composition constituting the B layer: a composition comprising 90% by weight of polymethylacrylene adipamide and 10% by weight of nylon 6.

The thickness ratio of each layer to the total thickness is B layer / A layer / B layer = 15% / 70% / 15%.

The oxygen permeability and pinhole number of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 2.

Experimental Examples 43 to 47 of a polyamide-based laminated biaxially stretched film satisfying Δnab and the requirements (4) and (5) in the claims are shown below.

[Experimental Example 43]

An unoriented sheet having the following constitution was obtained by using a two-kind three-layer coextrusion T-die apparatus. The total thickness of the unstretched sheet was 190 占 퐉 and the thickness ratio of each layer to the total thickness was 40% / 20% / 40% in the case of the layers B / A / B, , The extrusion resin temperature of the A layer is 270 占 폚, and the extrusion resin temperature of the B layer is 260 占 폚. Composition constituting the A layer: Composition composed of polymethoxy silylene adipamide (manufactured by Mitsubishi Gas Chemical Co., Ltd., RV = 2.65) = 100% by weight. 95% by weight of a composition constituting the layer B: nylon 6 (RV = 2.8, manufactured by Toyo Boseki Co., Ltd.) as a thermoplastic elastomer, a polyamide block copolymer (nylon 12 / polytetramethylene glycol copolymer, Box 4033, RV = 2.0).

The obtained non-stretched sheet was stretched 3.3 times in the longitudinal direction at a stretching temperature of 85 占 폚 by a roll, and then stretched 3.7 times in the transverse direction at a stretching temperature of 120 占 폚 by a tenter. In addition, the heat-setting treatment by the method described later was performed at 215 占 폚, the transverse relaxation treatment was carried out at 200 占 폚 at 6.7%, and the sheet was wound in a roll shape to obtain a biaxially stretched polyamide film having a width of 3,300 mm and a thickness of about 15 占 퐉 (Millrol).

[Heat fix treatment]

The heat fixing process was performed in a heat fixing apparatus having the structure as shown in Fig. The first to third zones are divided into four heat fixing zones, and the first to third zones are provided with eight plenum ducts (a to x), respectively. In the fourth zone, eight plenums The duct is installed. Each plenum duct is vertically provided at an interval of 400 mm with respect to the traveling direction of the film so as to be perpendicular to the traveling direction of the film. Then, hot air is blown to the stretched film from the hot air blow-out port (nozzle) of the plenum ducts thereof.

In Experimental Example 43, discontinuous bar-shaped shield plates (S, S) were attached to the hot air blow-out ports of fifteen plenum ducts a to o as shown in Fig. 4 is a top view of the open / closed position in which the shielding plates S, S ... are mounted on the hot air blowing outlets of the plenum ducts a to o. The shielding plates S, Is set so as to substantially coincide with the center of the width of the film passing through the opening and the dressing. The length of each shielding plate S (the dimension in the width direction of the film to be manufactured) is set such that the width gradually increases from the inlet to the outlet of the heat fixing apparatus (that is, widen toward the end) Has been adjusted. Table 4 shows the shielding rate (the shielding area of the hot air blowout port by the shield plate / the area of the hot air blowout port) of the hot air blowout port of each plenum duct of each of a to o. The shielding plate by the shield plate in Experimental Example 43 is referred to as " Solar A ".

In Experimental Example 43, the temperature and wind speed in the first to fourth zones of the heat fixing apparatus were adjusted as shown in Table 5. [ Further, in the temperature conditions and the wind speed conditions of the first to fourth zones of the heat fixing device of Experimental Example 43, the product of the temperature difference and the wind speed difference between adjacent heat fixing zones was 250 DEG C · m / s or less . The temperature and wind speed conditions in the first to fourth zones in Experimental Example 43 are set to " I condition ".

[Characteristic evaluation of film]

The film thus obtained was evaluated for its characteristics by the above-mentioned method. The evaluation results are shown in Tables 6 and 7.

[Experimental Example 44]

II extruder to increase the width of the unstretched film and change the shielding plate attached to the hot air blow-out port of each plenum duct of the heat fixing device to have a shielding rate as shown in Table 4, A millrol having a thickness of about 15 탆 and a width of 5,300 mm was wound in the same manner as in Experimental Example 43 except that the temperature and wind speeds in the first to fourth zones of the fixing device were changed as shown in Table 5. Thereafter, the film was evaluated for its characteristics by the above-described method. The evaluation results are shown in Tables 6 and 7. In addition, the shielding mode by the shield plate in Experimental Example 44 is referred to as "B sun", and the temperature and wind speed conditions in the first to fourth zones in Experimental Example 44 are referred to as "II conditions".

[Experimental Example 45]

The thickness of the unstretched sheet was increased to about 280 탆 by increasing the melt extrusion amount by the extruder to change the film thickness after heat fixation to about 25 탆 and changing the stretching operation in the longitudinal direction to a stretching operation of 3.0 times , A milrol having a thickness of about 25 占 퐉 and a width of 3,300 mm wound thereon was obtained. The properties of the film and the film roll were evaluated using a slit roll at the same position as in Experimental Example 43. [ The evaluation results are shown in Tables 6 and 7.

[Experimental Example 46]

A biaxially stretched film was obtained in the same manner as in Experimental Example 43 except that the structure of the unstretched sheet in Experimental Example 43 was changed as follows.

The total thickness of the unstretched sheet was 190 占 퐉 and the thickness ratio of each layer to the total thickness was 40% / 20% / 40% in the case of the layers B / A / B, , The extrusion resin temperature of the A layer is 270 占 폚, and the extrusion resin temperature of the B layer is 260 占 폚. 95% by weight of a composition constituting the layer A: 95% by weight of polymethoxy silylene adipamide (RV = 2.65, manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a thermoplastic elastomer, a polyamide block copolymer (nylon 12 / polytetramethylene glycol By weight, Arkemaase Pebbox 4033, RV = 2.0). Composition constituting the B layer: Composition comprising 100% by weight of nylon 6 (RV = 2.8, manufactured by Toyobo Co., Ltd.).

The properties of the film and the film roll were evaluated using a slit roll at the same position as in Experimental Example 43. [ The evaluation results are shown in Tables 6 and 7.

[Experimental Example 47]

A biaxially stretched film was obtained in the same manner as in Experimental Example 43 except that the structure of the unstretched sheet in Experimental Example 43 was changed as follows.

An unoriented sheet having the following constitution was obtained by using co-extrusion T die equipment of three kinds and five layers. The total thickness of the unstretched sheet is 190 占 퐉 and the thickness ratio of each layer to the total thickness is in the order of C layer / B layer / A layer / B layer / C layer / B layer / A layer / B layer / / C layer = 25% / 15% / 20% / 15% / 25% The extrusion resin temperature of the A layer is 270 占 폚 and the extrusion resin temperature of the B layer and the C layer is 260 占 폚. 95% by weight of a composition constituting the layer A: 95% by weight of polymethoxy silylene adipamide (RV = 2.65, manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a thermoplastic elastomer, a polyamide block copolymer (nylon 12 / polytetramethylene glycol By weight, Arkemaase Pebbox 4033, RV = 2.0). A composition constituting the B layer: 25% by weight of a composition consisting of 70% by weight of nylon 6 (RV = 2.8, manufactured by Toyobo Co., Ltd.) and polymethoxysilylene adipamide (RV = 2.65, manufactured by Mitsubishi Gas Chemical Co., And 5% by weight of a polyamide block copolymer (nylon 12 / polytetramethylene glycol copolymer, Arkema Pebax 4033, RV = 2.0) as a thermoplastic elastomer. Composition constituting the C layer: Composition composed of 100% by weight of nylon 6 (RV = 2.8, manufactured by Toyobo Co., Ltd.).

The properties of the film and the film roll were evaluated using the slit nozzle at the same position as in Experimental Example 43. [ The evaluation results are shown in Tables 6 and 7.

Hereinafter, Experimental Examples 48 to 50 are comparative experimental examples for Experimental Examples 43 to 47.

[Experimental Example 48]

Except that the heat shielding plate was not attached to the hot air blow-out port of each plenum duct and the temperature and wind speeds in the first to fourth zones of the heat fixing apparatus were changed as shown in Table 5, To obtain a milylol film of about 15 탆. The temperature and wind speed conditions in the first to fourth zones in Experimental Example 43 are set as " III conditions. &Quot; The properties of the film and the film were evaluated using a slit roll at the same position as in Experimental Example 43. The evaluation results are shown in Tables 6 and 7.

[Experimental Example 49]

The same procedure as in Experimental Example 44 was carried out except that the heat fixing was performed without attaching the shielding plate to the hot air blowout port of each plenum duct and the temperature and wind speeds in the first to fourth zones of the heat fixing apparatus were changed as shown in Table 5 To obtain a milylol film of about 15 탆. The temperature and wind speed conditions in the first to fourth zones in Experimental Example 49 are set as " IV conditions. &Quot; Then, using the slit roll in the same position as Experimental Example 44, the properties of the film and the film were evaluated. The evaluation results are shown in Tables 6 and 7.

[Experimental Example 50]

Except that the heat shielding plate was not attached to the hot air blow-out port of each plenum duct and the temperature and wind speeds in the first to fourth zones of the heat fixing apparatus were changed as shown in Table 5, To obtain a milylol film having a thickness of about 25 탆. The temperature and wind speed conditions in the first to fourth zones in Experimental Example 50 are referred to as " III conditions ". The properties of the film and the film were evaluated using a slit roll at the same position as in Experimental Example 43. The evaluation results are shown in Tables 6 and 7.

[Effects of Experimental Film]

It can be seen from Table 6 that all of the films of Experimental Examples 43 to 47 exhibit not only a small difference in heat shrinkage rate across the roll width (that is, a difference in heat shrinkage rate) but also a small amount of variation in heat shrinkage rate in the longitudinal direction, Is good and is suitable for post-processing. Moreover, it is finished beautifully without wrinkles of the sealing part when the bag is used. On the other hand, in the films of Experimental Examples 48 to 50, the difference in the heat shrinkage ratio over the entire width was large, and thus the passing property at the time of post-processing was poor, and the sealing portion was wrinkled when sealed.

Experimental Examples 51 to 53 in which the peel strength described in the claims satisfy 4.0 N / 15 mm or more are shown below for Experimental Examples 43 to 47.

[Experimental Example 51]

An unoriented sheet having the following constitution was obtained by using a two-kind three-layer coextrusion T-die apparatus. The total thickness of the unstretched sheet was 190 占 퐉 and the thickness ratio of each layer to the total thickness was 40% / 20% / 40% in the case of the layers B / A / B, , The extrusion resin temperature of the A layer is 270 占 폚, and the extrusion resin temperature of the B layer is 260 占 폚. Composition constituting the A layer: Composition composed of polymethoxy silylene adipamide (manufactured by Mitsubishi Gas Chemical Co., Ltd., RV = 2.65) = 100% by weight. 89% by weight of a composition constituting the B layer: nylon 6 (RV = 2.8, manufactured by Toyo Boseki K.K.) as a thermoplastic elastomer, a polyamide block copolymer (nylon 12 / polytetramethylene glycol copolymer, 5% by weight of polyvinylidene fluoride resin (trade name: Box 4033, RV = 2.0), and 6% by weight of polymethoxy silylene adipamide (manufactured by Mitsubishi Gas Chemical Company, RV = 2.65).

The obtained non-stretched sheet was stretched 3.3 times in the longitudinal direction at a stretching temperature of 85 占 폚 by a roll, and then stretched 3.7 times in the transverse direction at a stretching temperature of 120 占 폚 by a tenter. Further, heat-setting treatment by a method described later was carried out at 215 占 폚, transverse relaxation treatment was carried out at 200 占 폚 at 6.7%, and the sheet was rolled up into a roll to obtain a biaxially stretched polyamide film having a width of 3,300 mm and a thickness of about 15 占 퐉 Millrol) was prepared.

[Heat fix treatment]

The heat fixing process was performed in a heat fixing apparatus having the structure as shown in Fig. The first to third zones are divided into four heat fixing zones, and the first to third zones are provided with eight plenum ducts (a to x), respectively. In the fourth zone, eight plenums The duct is installed. Each of the plenum ducts is vertically provided at an interval of 400 mm with respect to the traveling direction of the film so as to be perpendicular to the traveling direction of the film. Then, hot air is blown to the stretched film from the hot air blow-out port (nozzle) of the plenum ducts thereof.

In Experimental Example 51, discontinuous bar-shaped shielding plates S, S ... were attached to the hot air blow-out ports of fifteen plenum ducts a to o as shown in Fig. 4 is a top view of the open / closed position in which the shielding plates S, S ... are mounted on the hot air blowing outlets of the plenum ducts a to o. The shielding plates S, Is set so as to substantially coincide with the center of the width of the film passing through the opening and the dressing. The length of each shielding plate S (the dimension in the width direction of the film to be manufactured) is set such that the width gradually increases from the inlet to the outlet of the heat fixing apparatus (that is, widen toward the end) Has been adjusted. Table 9 shows the shielding rate (the shielding area of the hot air blowout port by the shield plate / the area of the hot air blowout port) of the hot air blowout port of each plenum duct of each of a to o. In addition, the shielding mode by the shield plate in Experimental Example 51 is referred to as " Solar A ".

In Experimental Example 51, the temperature and wind speeds of the first to fourth zones of the heat fixing apparatus were adjusted as shown in Table 10. Further, in the temperature conditions and the wind speed conditions of the first to fourth zones of the heat fixing device of Experimental Example 51, the product of the temperature difference and the wind speed difference between the adjacent heat fixing zones was 250 ° C · m / s or less Respectively. The temperature and wind speed conditions in the first to fourth zones in Experimental Example 51 are set to " I condition ".

[Characteristic evaluation of film]

The film thus obtained was evaluated for its characteristics by the above-mentioned method. The evaluation results are shown in Tables 11 and 12.

[Experimental Example 52]

The width of the unstretched film was increased by increasing the amount of melt extrusion by the extruder and the shielding plate attached to the hot air blowout port of each plenum duct of the heat fixing device was changed to have a shielding rate as shown in Table 9, A milrol having a thickness of about 15 탆 and a width of 5,300 mm was wound in the same manner as in Experimental Example 51 except that the temperatures and wind speeds in the first to fourth zones of the apparatus were changed as shown in Table 10. Thereafter, the film was evaluated for its characteristics by the above-described method. The evaluation results are shown in Tables 11 and 12. In addition, the shielding plate by the shield plate in Experimental Example 52 is referred to as " B Sun ", and the temperature and wind speed conditions in the first to fourth zones in Experimental Example 52 are referred to as " II conditions ".

[Experimental Example 53]

The thickness of the unstretched sheet was increased to about 280 탆 by increasing the melt extrusion amount by the extruder to change the film thickness after heat fixation to about 25 탆 and changing the stretching operation in the longitudinal direction to a stretching operation of 3.0 times , A milrol having a thickness of about 25 占 퐉 and a width of 3,300 mm wound thereon was obtained. The properties of the film and the film roll were evaluated using a slit roll at the same position as in Experimental Example 51. [ The evaluation results are shown in Tables 11 and 12.

Comparative Examples 54 to 56 for Experimental Examples 51 to 53 will be described below.

[Experimental Example 54]

The same procedure as in Experimental Example 51 was repeated except that the heat shielding plate was not attached to the hot air blow-out port of each plenum duct and the temperature and wind speeds in the first to fourth zones of the heat fixing apparatus were changed as shown in Table 10 To obtain a milylol film of about 15 탆. The temperature and wind speed conditions in the first to fourth zones in Experimental Example 54 are defined as " III conditions. &Quot; The properties of the film and the film were evaluated using a slit roll at the same position as in Experimental Example 51. [ The evaluation results are shown in Tables 11 and 12.

[Experimental Example 55]

Except that the shielding plate was not mounted on the hot air blow-out port of each plenum duct and heat was fixed, and the temperature and wind speeds in the first to fourth zones of the heat fixing apparatus were changed as shown in Table 10, To obtain a milylol film of about 15 탆. The temperature and wind speed conditions in the first to fourth zones in Experimental Example 55 are defined as " IV conditions. &Quot; The properties of the film and the film were evaluated using a slit roll at the same position as in Experimental Example 52. [ The evaluation results are shown in Tables 11 and 12.

[Experimental Example 56]

The same procedure as in Experimental Example 51 was repeated except that the heat shielding plate was not attached to the hot air blow-out port of each plenum duct and the temperature and wind speeds in the first to fourth zones of the heat fixing apparatus were changed as shown in Table 10 To obtain a milylol film having a thickness of about 25 탆. The temperature and wind speed conditions in the first to fourth zones in Experimental Example 56 are referred to as " III conditions ". The properties of the film and the film were evaluated using a slit roll at the same position as in Experimental Example 51. [ The evaluation results are shown in Tables 11 and 12.

[Effects of Experimental Film]

It can be seen from Table 11 that all of the films of Experimental Examples 51 to 53 exhibit not only a small difference in heat shrinkage rate across the roll width (that is, a difference in heat shrinkage rate) but also a small amount of variation in heat shrinkage rate in the longitudinal direction, Is good and is suitable for post-processing. Moreover, it is finished beautifully without wrinkles of the sealing part when the bag is used. On the other hand, in the films of Experimental Examples 54 to 56, the difference in the heat shrinkage ratio over the entire width was large, so that the passing property at the time of post-processing was poor, and the sealing portion was wrinkled when sealed.

Experimental Examples 57 to 65 of a polyamide laminated biaxially stretched film having a thickness unevenness as claimed in the claims satisfying 3 to 10% are shown below.

[Experimental Example 57]

An unoriented sheet having the following constitution was obtained by using a two-kind three-layer coextrusion T-die apparatus. The total thickness of the unstretched sheet was 190 占 퐉 and the thickness ratio of each layer to the total thickness was 40% / 20% / 40% in the case of the layers B / A / B, , The extrusion resin temperature of the A layer is 270 占 폚, and the extrusion resin temperature of the B layer is 260 占 폚. Composition constituting the A layer: Composition composed of polymethoxy silylene adipamide (manufactured by Mitsubishi Gas Chemical Co., Ltd., RV = 2.65) = 100% by weight. 95% by weight of a composition constituting the layer B: nylon 6 (RV = 2.8, manufactured by Toyo Boseki Co., Ltd.) as a thermoplastic elastomer, a polyamide block copolymer (nylon 12 / polytetramethylene glycol copolymer, Box 4033, RV = 2.0). The take-up speed (roll rotation speed) of the unstretched sheet was about 66 m / min. At that time, the air gap at the time of winding the molten resin on the metal roll was adjusted to 40 mm, and a multi-needle electrode provided with a needle-like body of 1.5 mmø A negative charge of direct current was applied to the molten resin (sheet product), and the molten resin was electrostatically adhered to the metal roll by discharging the streamer corona. In addition, in the streamer corona discharge, the periphery of the electrode and the metal roll is surrounded by a wall member and shielded from the outside, the humidity around the multi-needle electrode is maintained at about 75% RH, and the temperature around the multi- Gt; 45 C. < / RTI > When the molten resin is wound around the metal roll, the portion where the molten resin is in contact with the metal roll is suctioned in a direction opposite to the direction in which the resin is wound by using a burr box over the entire width of the molten resin Thereby promoting adhesion of the molten resin to the metal roll. The suction wind speed of the buzzing box was adjusted to 5.0 ± 0.5 m / sec over the entire width of the suction port (ie, the entire width of the molten resin). Further, in the production of the undrawn film described above, adhesion of the oligomer to the multi-needle electrode was not observed, and the electrostatic adhesion state was very stable.

The obtained non-stretched sheet was stretched 3.3 times in the longitudinal direction at a stretching temperature of 85 占 폚 by a roll, and then stretched 3.7 times in the transverse direction at a stretching temperature of 120 占 폚 by a tenter. And further heat-set at a temperature of 215 캜 and subjected to a thermal relaxation treatment of 5%, whereby a biaxially stretched film having an average thickness of 15 탆 was produced. In addition, corona discharge treatment was performed on the surface of the B layer on the side of 40 占 퐉 of the linear low-density polyethylene film (L-LDPE film: L6102 made by Toyobo Co., Ltd.) and on the side subjected to the dry lamination. The oxygen permeability, pinhole number and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 13.

[Experimental Example 58]

A biaxially stretched film was obtained in the same manner as in Experimental Example 57 except that the description of Experimental Example 57 was changed as follows.

Composition constituting the B layer: 98% by weight of nylon 6 and 2% by weight of polyamide block copolymer.

The oxygen permeability, pinhole number and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 13.

[Experimental Example 59]

A biaxially stretched film was obtained in the same manner as in Experimental Example 57 except that the description of Experimental Example 57 was changed as follows.

Composition constituting the B layer: a composition comprising 99% by weight of nylon 6 and 1% by weight of a polyamide block copolymer.

The oxygen permeability, pinhole number and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 13.

[Experimental Example 60]

A biaxially stretched film was obtained in the same manner as in Experimental Example 57 except that the description of Experimental Example 57 was changed as follows.

Composition constituting the B layer: 98% by weight of nylon 6 and 2% by weight of polyamide block copolymer.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 41% / 18% / 41%.

The oxygen permeability, pinhole number and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 13.

[Experimental Example 61]

A biaxially stretched film was obtained in the same manner as in Experimental Example 57 except that the description of Experimental Example 57 was changed as follows.

Composition constituting the B layer: a composition comprising 97% by weight of nylon 6 and 3% by weight of a polyamide block copolymer.

The thickness ratio of each layer to the total thickness is B layer / A layer / B layer = 39% / 22% / 39%.

The oxygen permeability, pinhole number and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 13.

[Experimental Example 62]

A biaxially stretched film was obtained in the same manner as in Experimental Example 57 except that the description of Experimental Example 57 was changed as follows.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 43% / 14% / 43%.

The oxygen permeability, pinhole number and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 13.

[Experimental Example 63]

A biaxially stretched film was obtained in the same manner as in Experimental Example 57 except that the description of Experimental Example 57 was changed as follows.

Composition constituting the B layer: 98% by weight of nylon 6 and 2% by weight of polyamide block copolymer.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 36% / 28% / 36%.

The oxygen permeability, pinhole number and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 13.

[Experimental Example 64]

A biaxially stretched film was obtained in the same manner as in Experimental Example 57 except that the description of Experimental Example 57 was changed as follows.

Composition comprising B layer: 99% by weight of nylon 6 and 1% by weight of polyamide block copolymer.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 43% / 14% / 43%.

The oxygen permeability, pinhole number and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 13.

[Experimental Example 65]

A biaxially stretched film was obtained in the same manner as in Experimental Example 57 except that the description of Experimental Example 57 was changed as follows.

Composition constituting the B layer: a composition comprising 93% by weight of nylon 6 and 7% by weight of a polyamide block copolymer.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 36% / 28% / 36%.

The oxygen permeability, pinhole number and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 13.

Comparative Experimental Examples 66 to 72 for Experimental Examples 57 to 65 are described below.

[Experimental Example 66]

A biaxially stretched film was obtained in the same manner as in Experimental Example 57 except that the description of Experimental Example 57 was changed as follows.

Composition constituting layer B: nylon 6 Composition of 100% by weight.

The oxygen permeability, pinhole number and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 13.

[Experimental Example 67]

A biaxially stretched film was obtained in the same manner as in Experimental Example 57 except that the description of Experimental Example 57 was changed as follows.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 30% / 40% / 30%.

The oxygen permeability, pinhole number and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 13.

[Experimental Example 68]

A biaxially stretched film was obtained in the same manner as in Experimental Example 57 except that the description of Experimental Example 57 was changed as follows.

Composition constituting Layer A: 80% by weight of polymethylacrylene adipamide and 20% by weight of nylon 6.

The oxygen permeability, pinhole number and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 13.

[Experimental Example 69]

A biaxially stretched film was obtained in the same manner as in Experimental Example 57 except that the description of Experimental Example 57 was changed as follows.

Composition constituting Layer A: 80% by weight of polymethylacrylene adipamide and 20% by weight of nylon 6.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 20% / 60% / 20%.

The oxygen permeability, pinhole number and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 13.

[Experimental Example 70]

A biaxially stretched film was obtained in the same manner as in Experimental Example 57 except that the description of Experimental Example 57 was changed as follows.

Composition constituting Layer A: 80% by weight of polymethylacrylene adipamide and 20% by weight of nylon 6.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 30% / 40% / 30%.

The oxygen permeability, pinhole number and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 13.

[Experimental Example 71]

A biaxially stretched film was obtained in the same manner as in Experimental Example 57 except that the description of Experimental Example 57 was changed as follows.

Composition constituting layer A: Composition comprising 90% by weight of polymethoxy silylene adipamide and 10% by weight of polyamide block copolymer.

Composition constituting layer B: nylon 6 Composition of 100% by weight.

The oxygen permeability, pinhole number and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 13.

[Experimental Example 72]

When the molten resin was electrostatically adhered to the metal roll in the base material of Experimental Example 57, the electrode was changed to a wire of 0.5 mm while keeping the rotation speed of the metal roll at about 66 m / min as in Experimental Example 57 , And a direct negative current of 100 mA at 11 ± 1.1 kV was applied to the molten resin to cause glow discharge and the biaxially oriented film was obtained in the same manner as in Experimental Example 57,

The oxygen permeability, pinhole number and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Table 13.

Experimental Examples 73 to 84 each of which satisfies the peel strength 4.0 N / 15 mm or more described in the claims are shown below for Experimental Examples 57 to 65.

[Experimental Example 73]

An unoriented sheet having the following constitution was obtained by using a two-kind three-layer coextrusion T-die apparatus. The total thickness of the unstretched sheet was 190 占 퐉 and the thickness ratio of each layer to the total thickness was 40% / 20% / 40% in the case of the layers B / A / B, , The extrusion resin temperature of the A layer is 270 占 폚, and the extrusion resin temperature of the B layer is 260 占 폚. Composition constituting the A layer: Composition composed of polymethoxy silylene adipamide (manufactured by Mitsubishi Gas Chemical Co., Ltd., RV = 2.65) = 100% by weight. 89% by weight of a composition constituting the B layer: nylon 6 (RV = 2.8, manufactured by Toyo Boseki K.K.) as a thermoplastic elastomer, a polyamide block copolymer (nylon 12 / polytetramethylene glycol copolymer, 5% by weight of polyvinylidene fluoride resin (trade name: Box 4033, RV = 2.0), and 6% by weight of polymethoxy silylene adipamide (manufactured by Mitsubishi Gas Chemical Company, RV = 2.65). The take-up speed (roll rotation speed) of the unstretched sheet was about 66 m / min. At this time, the air gap at the time of winding the molten resin on the metal roll was adjusted to 40 mm, and a DC negative charge of 100 mA at 11 ± 1.1 kv was melted by a multi- Was applied to a resin (sheet), and the molten resin was electrostatically adhered to the metal roll by discharging the streamer corona. In addition, in the streamer corona discharge, the periphery of the electrode and the metal roll is surrounded by a wall member and shielded from the outside, the humidity around the multi-needle electrode is maintained at about 75% RH, and the temperature around the multi- Gt; 45 C. < / RTI > When the molten resin is wound around the metal roll, the portion where the molten resin is in contact with the metal roll is suctioned in a direction opposite to the direction in which the resin is wound by using a burr box over the entire width of the molten resin Thereby promoting adhesion of the molten resin to the metal roll. The suction wind speed of the buzzing box was adjusted to 5.0 ± 0.5 m / sec over the entire width of the suction port (ie, the entire width of the molten resin). Further, in the production of the undrawn film described above, adhesion of the oligomer to the multi-needle electrode was not observed, and the electrostatic adhesion state was very stable.

The obtained non-stretched sheet was stretched 3.3 times in the longitudinal direction at a stretching temperature of 85 占 폚 by a roll, and then stretched 3.7 times in the transverse direction at a stretching temperature of 120 占 폚 by a tenter. And further heat-set at a temperature of 215 캜 and subjected to a thermal relaxation treatment of 5%, whereby a biaxially stretched film having an average thickness of 15 탆 was produced. In addition, corona discharge treatment was performed on the surface of the B layer on the side of 40 占 퐉 of the linear low-density polyethylene film (L-LDPE film: L6102 made by Toyobo Co., Ltd.) and on the side subjected to the dry lamination. The oxygen permeability, pinhole number, peel strength and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. Table 14 shows the results.

[Experimental Example 74]

A biaxially stretched film was obtained in the same manner as in Experimental Example 73 except that the description of Experimental Example 73 was changed as follows.

Composition constituting the layer B: a composition consisting of 95% by weight of nylon 6, 2% by weight of a polyamide block copolymer and 3% by weight of polymethoxy silylene adipamide.

The oxygen permeability, pinhole number, peel strength and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. Table 14 shows the results.

[Experimental Example 75]

A biaxially stretched film was obtained in the same manner as in Experimental Example 73 except that the description of Experimental Example 73 was changed as follows.

Composition constituting the B layer: a composition comprising 97% by weight of nylon 6, 1% by weight of a polyamide block copolymer, and 2% by weight of polymethoxy silylene adipamide.

The oxygen permeability, pinhole number, peel strength and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. Table 14 shows the results.

[Experimental Example 76]

A biaxially stretched film was obtained in the same manner as in Experimental Example 73 except that the description of Experimental Example 73 was changed as follows.

Composition constituting the layer B: a composition consisting of 95% by weight of nylon 6, 2% by weight of a polyamide block copolymer and 3% by weight of polymethoxy silylene adipamide.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 41% / 18% / 41%.

The oxygen permeability, pinhole number, peel strength and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. Table 14 shows the results.

[Experimental Example 77]

A biaxially stretched film was obtained in the same manner as in Experimental Example 73 except that the description of Experimental Example 73 was changed as follows.

Composition comprising B layer: 92% by weight of nylon 6, 3% by weight of polyamide block copolymer and 5% by weight of polymethylacrylene adipamide.

The thickness ratio of each layer to the total thickness is B layer / A layer / B layer = 39% / 22% / 39%.

The oxygen permeability, pinhole number, peel strength and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. Table 14 shows the results.

[Experimental Example 78]

A biaxially stretched film was obtained in the same manner as in Experimental Example 73 except that the description of Experimental Example 73 was changed as follows.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 43% / 14% / 43%.

The oxygen permeability, pinhole number, peel strength and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. Table 14 shows the results.

[Experimental Example 79]

A biaxially stretched film was obtained in the same manner as in Experimental Example 73 except that the description of Experimental Example 73 was changed as follows.

Composition constituting the layer B: a composition consisting of 95% by weight of nylon 6, 2% by weight of a polyamide block copolymer and 3% by weight of polymethoxy silylene adipamide.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 36% / 28% / 36%.

The oxygen permeability, pinhole number, peel strength and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. Table 14 shows the results.

[Experimental Example 80]

A biaxially stretched film was obtained in the same manner as in Experimental Example 73 except that the description of Experimental Example 73 was changed as follows.

Composition constituting the B layer: a composition comprising 97% by weight of nylon 6, 1% by weight of a polyamide block copolymer, and 2% by weight of polymethoxy silylene adipamide.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 43% / 14% / 43%.

The oxygen permeability, pinhole number, peel strength and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. Table 14 shows the results.

[Experimental Example 81]

A biaxially stretched film was obtained in the same manner as in Experimental Example 73 except that the description of Experimental Example 73 was changed as follows.

Composition constituting the B layer: Composition composed of 83% by weight of nylon 6, 7% by weight of polyamide block copolymer and 10% by weight of polymethoxy silylene adipamide.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 36% / 28% / 36%.

The oxygen permeability, pinhole number, peel strength and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. Table 14 shows the results.

[Experimental Example 82]

A biaxially stretched film was obtained in the same manner as in Experimental Example 73 except that the description of Experimental Example 73 was changed as follows.

Composition constituting the B layer: a composition consisting of 93% by weight of nylon 6, 5% by weight of a polyamide block copolymer and 2% by weight of polymethoxy silylene adipamide.

The oxygen permeability, pinhole number, peel strength and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. Table 14 shows the results.

[Experimental Example 83]

A biaxially stretched film was obtained in the same manner as in Experimental Example 73 except that the description of Experimental Example 73 was changed as follows.

Composition comprising B layer: 84% by weight of nylon 6, 5% by weight of polyamide block copolymer and 11% by weight of polymethoxy silylene adipamide.

The oxygen permeability, pinhole number, peel strength and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. Table 14 shows the results.

[Experimental Example 84]

A biaxially stretched film was obtained in the same manner as in Experimental Example 73 except that the description of Experimental Example 73 was changed as follows.

Composition constituting the B layer: a composition consisting of 98% by weight of nylon 6, 1% by weight of a polyamide block copolymer and 1% by weight of polymethoxy silylene adipamide.

The oxygen permeability, pinhole number, peel strength and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. Table 14 shows the results.

Comparative Experiments 85 to 94 for Experimental Examples 73 to 84 will be described below.

[Experimental Example 85]

A biaxially stretched film was obtained in the same manner as in Experimental Example 73 except that the description of Experimental Example 73 was changed as follows.

Composition constituting layer B: nylon 6 Composition of 100% by weight.

The oxygen permeability, pinhole number, peel strength and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. Table 14 shows the results.

[Experimental Example 86]

A biaxially stretched film was obtained in the same manner as in Experimental Example 73 except that the description of Experimental Example 73 was changed as follows.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 30% / 40% / 30%.

The oxygen permeability, pinhole number, peel strength and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. Table 14 shows the results.

[Experimental Example 87]

A biaxially stretched film was obtained in the same manner as in Experimental Example 73 except that the description of Experimental Example 73 was changed as follows.

Composition constituting Layer A: 80% by weight of polymethylacrylene adipamide and 20% by weight of nylon 6.

The oxygen permeability, pinhole number, peel strength and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. Table 14 shows the results.

[Experimental Example 88]

A biaxially stretched film was obtained in the same manner as in Experimental Example 73 except that the description of Experimental Example 73 was changed as follows.

Composition constituting Layer A: 80% by weight of polymethylacrylene adipamide and 20% by weight of nylon 6.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 20% / 60% / 20%.

The oxygen permeability, pinhole number, peel strength and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. Table 14 shows the results.

[Experimental Example 89]

A biaxially stretched film was obtained in the same manner as in Experimental Example 73 except that the description of Experimental Example 73 was changed as follows.

Composition constituting Layer A: 80% by weight of polymethylacrylene adipamide and 20% by weight of nylon 6.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 30% / 40% / 30%.

The oxygen permeability, pinhole number, peel strength and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. Table 14 shows the results.

[Experimental Example 90]

A biaxially stretched film was obtained in the same manner as in Experimental Example 73 except that the description of Experimental Example 73 was changed as follows.

Composition constituting the B layer: a composition comprising 95% by weight of nylon 6 and 5% by weight of a polyamide block copolymer.

The oxygen permeability, pinhole number, peel strength and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. Table 14 shows the results.

[Experimental Example 91]

A biaxially stretched film was obtained in the same manner as in Experimental Example 73 except that the description of Experimental Example 73 was changed as follows.

Composition constituting the B layer: a composition comprising 99% by weight of nylon 6 and 1% by weight of a polyamide block copolymer.

The oxygen permeability, pinhole number, peel strength and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. Table 14 shows the results.

[Experimental Example 92]

A biaxially stretched film was obtained in the same manner as in Experimental Example 73 except that the description of Experimental Example 73 was changed as follows.

Composition comprising B layer: 95% by weight of nylon 6 and 5% by weight of polymethoxy silylene adipamide.

The oxygen permeability, pinhole number, peel strength and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. Table 14 shows the results.

[Experimental Example 93]

A biaxially stretched film was obtained in the same manner as in Experimental Example 73 except that the description of Experimental Example 73 was changed as follows.

Composition constituting layer A: Composition comprising 90% by weight of polymethoxy silylene adipamide and 10% by weight of polyamide block copolymer.

Composition constituting layer B: nylon 6 Composition of 100% by weight.

The oxygen permeability, pinhole number, peel strength and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability, vibration durability, and rupture resistance. Table 14 shows the results.

[Experimental Example 94]

When the molten resin was electrostatically adhered to the metal roll in the base material of Experimental Example 73, the electrode was changed to a wire of 0.5 mm while keeping the rotation speed of the metal roll at about 66 m / min as in Experimental Example 73 A biaxially stretched film was obtained in the same manner as in Experimental Example 73, except that a DC negative charge of 100 mA at 11 ± 1.1 kV was applied to the molten resin to cause glow discharge and no suction by a burping box was performed.

The oxygen permeability, pinhole number, peel strength and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. Table 14 shows the results.

Next, Experimental Examples 95 to 97 of preferred embodiments in which the adhesive modifying coating applied to the film described in the claims is applied will be described.

[Experimental Example 95]

≪ Adjustment of Coating Liquid for Formation of Adhesive Modifying Film (Copolymer Polyester Aqueous Dispersion)

466 parts of dimethylterephthalate, 466 parts of dimethyl isophthalate, 401 parts of neopentyl glycol, 443 parts of ethylene glycol, and 0.52 parts of tetra-n-butyl titanate were added to a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser And the ester exchange reaction was carried out at 160 to 220 DEG C over 4 hours. Subsequently, 23 parts of fumaric acid was added and the temperature was raised from 200 占 폚 to 220 占 폚 over 1 hour to carry out an esterification reaction. Then, the temperature was raised to 255 ° C, the pressure in the reaction system was gradually reduced, and the reaction was carried out with stirring under a reduced pressure of 0.2 mmHg for 1 hour and 30 minutes to obtain a polyester. The resulting polyester was light yellow transparent and had a glass transition temperature of 60 占 폚 and a weight average molecular weight of 12,000. The composition obtained by NMR measurement and the like was as follows.

Dicarboxylic acid component

Terephthalic acid 48 mol%

48 mol% of isophthalic acid

4 mol% fumaric acid

Diol component

Neopentyl glycol 50 mol%

50 mol% of ethylene glycol

75 parts of the above polyester resin, 56 parts of methyl ethyl ketone and 19 parts of isopropyl alcohol were placed in a reactor equipped with a stirrer, a thermometer, a refluxing apparatus and a quantitative dropping device, and heated and stirred at 65 DEG C to dissolve the resin. After the resin was completely dissolved, a solution of 17.5 parts of methacrylic acid and 7.5 parts of ethyl acrylate and 1.2 parts of azobisdimethylvaleronitrile in 25 parts of methyl ethyl ketone was added dropwise to the polyester solution at 0.2 ml / min. Stirring was continued for an additional 2 hours. After performing analytical sampling (5 g) from the reaction solution, 300 parts of water and 25 parts of triethylamine were added to the reaction solution, and the mixture was stirred for 1 hour to adjust the dispersion of the grafted polyester. Thereafter, the temperature of the obtained dispersion was raised to 100 캜, and methyl ethyl ketone, isopropyl alcohol and excess triethylamine were removed by distillation to obtain a copolymer polyester aqueous dispersion.

The obtained dispersion was white and had an average particle size of 300 nm and a B-type viscosity at 25 DEG C of 50 cps. 1.25 g of heavy water was added to 5 g of the dispersion to adjust the solid concentration to 20 wt%, DSS was added, and 125 MHz 13 C-NMR was measured. The half-width of the signal (160-175 ppm) of the carbonyl carbon of the polyester main chain is ∞ (no signal is detected), and the half-width of the signal (181-186 ppm) of the carbonyl carbon of the methacrylic acid in the graft portion is 110 Hz. The solution sampled at the end of the grafting reaction was dried under vacuum at 100 DEG C for 8 hours to measure the acid value, the graft efficiency of the polyester (measurement of NMR), and the measurement of the graft portion by hydrolysis And the molecular weight was measured. The acid value of the solid was 2,300 eq. In the measurement of 1 H-NMR, it was confirmed that the grafting efficiency of the polyester was 100% since no signal derived from fumaric acid (? = 6.8-6.9 ppm, doublet) was detected at all. The graft portion had a weight average molecular weight of 10,000.

Then, the dispersion thus obtained was diluted with water to a solid concentration of 5% to obtain a coating liquid (copolymerized polyester aqueous dispersion) A for forming an adhesive property modifying film.

≪ Preparation of polyamide-based laminated biaxially stretched film >

An unoriented sheet having the following constitution was obtained by using a two-kind three-layer coextrusion T-die apparatus. The total thickness of the unstretched sheet was 210 占 퐉 and the ratio of the thickness of each layer to the total thickness was 40% / 20% / 40% of the B / A / B layers. , The extrusion resin temperature of the A layer is 270 占 폚, and the extrusion resin temperature of the B layer is 260 占 폚. Composition constituting the A layer: Composition composed of polymethoxy silylene adipamide (manufactured by Mitsubishi Gas Chemical Co., Ltd., RV = 2.65) = 100% by weight. 95% by weight of a composition constituting the layer B: nylon 6 (RV = 2.8, manufactured by Toyo Boseki Co., Ltd.) as a thermoplastic elastomer, a polyamide block copolymer (nylon 12 / polytetramethylene glycol copolymer, Box 4033, RV = 2.0).

Then, the obtained undrawn film was subjected to longitudinal drawing (first kind drawing) at a draw temperature of about 85 캜 at a drawing temperature of about 85 캜 by a roll made of Teflon (registered trademark) And was subjected to longitudinal drawing (second-type drawing) at a magnification of 1.6 times. Subsequently, the above-mentioned coating fluid for forming an adhesion modifying film (copolymerized polyester aqueous dispersion) A was continuously coated on the surface of the film after longitudinal drawing in a gravure manner, and the coating liquid was dried on a roll controlled at 150 캜 . The application amount of the coating liquid was adjusted so as to form an adhesive modified film of 0.2 g / m < 2 >.

After applying the adhesive modifying coating to the surface of the film after the longitudinal stretching as described above, the longitudinally stretched sheet is continuously led to the tenter, transversely stretched at about 130 占 폚 to 4.0 times, heat set at about 210 占 폚 % After the transverse relaxation treatment, cooling was performed, and both edge portions were cut off to produce a biaxially stretched film of about 15 탆. Further, corona discharge treatment was carried out on the surface of the adhesion modifying coating film which was dry laminated with 40 占 퐉 of a linear low-density polyethylene film (L-LDPE film: L6102 made by Toyobo Co., Ltd.). The oxygen permeability, pinhole number and peel strength of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Tables 15 to 16.

[Experimental Example 96]

≪ Adjustment of Coating Liquid for Formation of Adhesive Modifying Film (Copolymer Polyester Aqueous Dispersion)

A copolymer polyester aqueous dispersion was prepared in the same manner as in Experimental Example 95 except that 90 parts of the polyester resin obtained in Experimental Example 95, 7.0 parts of methacrylic acid, 3.0 parts of ethyl acrylate and 0.48 parts of azobisdimethylvaleronitrile were used . Then, the dispersion was diluted with water to a solid concentration of 5% to obtain a coating liquid (copolymerized polyester aqueous dispersion) B for forming an adhesive property modifying film.

Then, a polyamide-based laminated biaxially stretched film of Experimental Example 96 was obtained in the same manner as in Experimental Example 95, except that the coating liquid to be applied to the sheet after longitudinal drawing was changed to the above-mentioned coating liquid B. Then, the characteristics of the obtained film were evaluated in the same manner as in Experimental Example 95. The evaluation results are shown in Tables 15 to 16.

[Experimental Example 97]

≪ Adhesion Modification Coating Film Coating Solution (Copolymer Polyester Aqueous Dispersion) >

Except that 457 parts of dimethyl terephthalate, 452 parts of dimethyl isophthalate and 7.4 parts of dimethyl-5-sodium sulfoisophthalate were used and changed. The obtained polyester was light yellow transparent, had a glass transition temperature of 62 占 폚 and a weight average molecular weight of 12,000. The composition obtained by NMR measurement and the like was as follows.

Dicarboxylic acid component

Terephthalic acid 49 mol%

48.5 mol% of isophthalic acid

2.5 mol% of 5-sodium sulfoisophthalic acid

Diol component

Neopentyl glycol 50 mol%

50 mol% of ethylene glycol

100 parts of this polyester resin and a copolymer polyester aqueous dispersion not containing components such as methacrylic acid, ethyl acrylate, and azobisdimethylvaleronitrile were obtained in the same manner as in Experimental Example 95, And diluted with water to a solid concentration of 5% to obtain a coating fluid (copolymerized polyester aqueous dispersion) C for forming an adhesive property modifying film.

Then, a polyamide-based laminated biaxially stretched film of Experimental Example 97 was obtained in the same manner as in Experimental Example 95, except that the coating liquid applied to the sheet after longitudinal drawing was changed to the above-mentioned coating liquid C. Then, the characteristics of the obtained film were evaluated in the same manner as in Experimental Example 95. The evaluation results are shown in Tables 15 to 16.

Comparative Experimental Example 98 for Experimental Examples 95 to 97 will be described below.

[Experimental Example 98]

The procedure of Experimental Example 95 was repeated except that the step of applying the adhesive modifying coating to the sheet after longitudinal stretching was omitted and the transverse stretching was conducted in a tenter to obtain a polyamide based laminated biaxial stretching A film was obtained. Then, the properties of the obtained film were evaluated by the same method as Experimental Example 95. The evaluation results are shown in Tables 15 to 16.

Experimental Examples 99 to 101, in which the peel strength described in claims is 4.0 N / 15 mm or more, are shown for Experiments 95 to 97 below.

[Experimental Example 99]

≪ Adjustment of Coating Liquid for Formation of Adhesive Modifying Film (Copolymer Polyester Aqueous Dispersion)

466 parts of dimethylterephthalate, 466 parts of dimethyl isophthalate, 401 parts of neopentyl glycol, 443 parts of ethylene glycol, and 0.52 parts of tetra-n-butyl titanate were added to a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser And the ester exchange reaction was carried out at 160 to 220 DEG C over 4 hours. Subsequently, 23 parts of fumaric acid was added and the temperature was raised from 200 占 폚 to 220 占 폚 over 1 hour to carry out an esterification reaction. Then, the temperature was raised to 255 ° C, the reaction system was gradually depressurized and reacted with stirring under a reduced pressure of 0.2 mmHg for 1 hour and 30 minutes to obtain a polyester. The resulting polyester was light yellow transparent and had a glass transition temperature of 60 占 폚 and a weight average molecular weight of 12,000. The composition obtained by NMR measurement and the like was as follows.

Dicarboxylic acid component

Terephthalic acid 48 mol%

48 mol% of isophthalic acid

4 mol% fumaric acid

Diol component

Neopentyl glycol 50 mol%

50 mol% of ethylene glycol

75 parts of the above polyester resin, 56 parts of methyl ethyl ketone and 19 parts of isopropyl alcohol were placed in a reactor equipped with a stirrer, a thermometer, a refluxing apparatus and a quantitative dropping device, and heated and stirred at 65 DEG C to dissolve the resin. After the resin was completely dissolved, a solution of 17.5 parts of methacrylic acid and 7.5 parts of ethyl acrylate and 1.2 parts of azobisdimethylvaleronitrile in 25 parts of methyl ethyl ketone was added dropwise to the polyester solution at 0.2 ml / min. Stirring was continued for an additional 2 hours. After performing analytical sampling (5 g) from the reaction solution, 300 parts of water and 25 parts of triethylamine were added to the reaction solution, and the mixture was stirred for 1 hour to adjust the dispersion of the grafted polyester. Thereafter, the temperature of the obtained dispersion was raised to 100 캜, and methyl ethyl ketone, isopropyl alcohol and excess triethylamine were removed by distillation to obtain a copolymer polyester aqueous dispersion.

The obtained dispersion was white and had an average particle size of 300 nm and a B-type viscosity at 25 DEG C of 50 cps. 1.25 g of heavy water was added to 5 g of the dispersion to adjust the solid concentration to 20 wt%, DSS was added, and 125 MHz 13 C-NMR was measured. The half-width of the signal (160-175 ppm) of the carbonyl carbon of the polyester main chain is ∞ (no signal is detected), and the half-width of the signal (181-186 ppm) of the carbonyl carbon of the methacrylic acid in the graft portion is 110 Hz. The solution sampled at the end of the grafting reaction was dried under vacuum at 100 DEG C for 8 hours to measure the acid value, the graft efficiency of the polyester (measurement of NMR), and the measurement of the graft portion by hydrolysis And the molecular weight was measured. The acid value of the solid was 2,300 eq. In the measurement of 1 H-NMR, it was confirmed that the grafting efficiency of the polyester was 100% since no signal derived from fumaric acid (? = 6.8-6.9 ppm, doublet) was detected at all. The graft portion had a weight average molecular weight of 10,000.

Then, the dispersion thus obtained was diluted with water to a solid concentration of 5% to obtain a coating liquid (copolymerized polyester aqueous dispersion) A for forming an adhesive property modifying film.

An unoriented sheet having the following constitution was obtained by using a two-kind three-layer coextrusion T-die apparatus. The total thickness of the unstretched sheet was 210 占 퐉 and the ratio of the thickness of each layer to the total thickness was 40% / 20% / 40% of the B / A / B layers. , The extrusion resin temperature of the A layer is 270 占 폚, and the extrusion resin temperature of the B layer is 260 占 폚. Composition constituting the A layer: Composition composed of polymethoxy silylene adipamide (manufactured by Mitsubishi Gas Chemical Co., Ltd., RV = 2.65) = 100% by weight. 95% by weight of a composition constituting the layer B: nylon 6 (RV = 2.8, manufactured by Toyo Boseki Co., Ltd.) as a thermoplastic elastomer, a polyamide block copolymer (nylon 12 / polytetramethylene glycol copolymer, 5% by weight of polyvinylidene fluoride resin (trade name: Box 4033, RV = 2.0), and 6% by weight of polymethoxy silylene adipamide (manufactured by Mitsubishi Gas Chemical Company, RV = 2.65).

Then, the obtained undrawn film was subjected to longitudinal drawing (first kind drawing) at a draw temperature of about 85 캜 at a drawing temperature of about 85 캜 by a roll made of Teflon (registered trademark) And was subjected to longitudinal drawing (second-type drawing) at a magnification of 1.6 times. Subsequently, the above-mentioned coating fluid for forming an adhesion modifying film (copolymerized polyester aqueous dispersion) A was continuously coated on the surface of the film after longitudinal drawing in a gravure manner, and the coating liquid was dried on a roll controlled at 150 캜 . The application amount of the coating liquid was adjusted so as to form an adhesive modified film of 0.2 g / m < 2 >.

After applying the adhesive modifying coating to the surface of the film after longitudinally stretching as described above, the longitudinally stretched sheet was continuously led to a tenter, transversely stretched at about 130 占 폚 to 4.0 times, fixed at 210 占 폚 to 5.0 % After the transverse relaxation treatment, cooling was performed, and both edge portions were cut off to produce a biaxially stretched film of about 15 탆. Further, corona discharge treatment was carried out on the surface of the adhesion modifying coating film which was dry laminated with 40 占 퐉 of a linear low-density polyethylene film (L-LDPE film: L6102 made by Toyobo Co., Ltd.). The oxygen permeability, pinhole number and peel strength of the obtained biaxially stretched film were measured. Further, the packaging pouch made of the obtained film was tested for storage stability and vibration durability. The results are shown in Tables 17 to 18.

[Experimental Example 100]

≪ Adjustment of Coating Liquid for Formation of Adhesive Modifying Film (Copolymer Polyester Aqueous Dispersion)

A copolymer polyester aqueous dispersion was prepared in the same manner as in Experimental Example 99 except that 90 parts of the polyester resin obtained in Experimental Example 99, 7.0 parts of methacrylic acid, 3.0 parts of ethyl acrylate and 0.48 parts of azobisdimethylvaleronitrile were used . Then, the dispersion was diluted with water to a solid concentration of 5% to obtain a coating liquid (copolymerized polyester aqueous dispersion) B for forming an adhesive property modifying film.

Then, a polyamide-based laminated biaxially stretched film of Experimental Example 100 was obtained in the same manner as in Experimental Example 99 except that the coating liquid to be applied to the sheet after longitudinal drawing was changed to the above-mentioned coating liquid B. Then, the properties of the obtained film were evaluated by the same method as in Experimental Example 99. The evaluation results are shown in Tables 17 to 18.

[Experimental Example 101]

≪ Adjustment of Coating Liquid for Formation of Adhesive Modifying Film (Copolymer Polyester Aqueous Dispersion)

Except that 457 parts of dimethyl terephthalate, 452 parts of dimethyl isophthalate and 7.4 parts of dimethyl-5-sodium sulfoisophthalate were used and changed, and polyester was obtained in the same manner as in Experimental Example 99. The obtained polyester was light yellow transparent, had a glass transition temperature of 62 占 폚 and a weight average molecular weight of 12,000. The composition obtained by NMR measurement and the like was as follows.

Dicarboxylic acid component

Terephthalic acid 49 mol%

48.5 mol% of isophthalic acid

2.5 mol% of 5-sodium sulfoisophthalic acid

Diol component

Neopentyl glycol 50 mol%

50 mol% of ethylene glycol

100 parts of this polyester resin, and a copolymer polyester aqueous dispersion not containing components such as methacrylic acid, ethyl acrylate, and azobisdimethylvaleronitrile were obtained in the same manner as in Experimental Example 99, And diluted with water to a solid concentration of 5% to obtain a coating fluid (copolymerized polyester aqueous dispersion) C for forming an adhesive property modifying film.

Then, a polyamide-based laminated biaxially stretched film of Experimental Example 101 was obtained in the same manner as in Experimental Example 99 except that the coating liquid applied to the sheet after longitudinal drawing was changed to the above-mentioned coating liquid C. Then, the properties of the obtained film were evaluated by the same method as in Experimental Example 99. The evaluation results are shown in Tables 17 to 18.

Hereinafter, Comparative Example 102 for Experimental Examples 99 to 101 will be described.

[Experimental Example 102]

The procedure of Experimental Example 99 was repeated except that the step of applying the adhesive modifying coating to the sheet after longitudinal stretching was omitted and the transverse stretching was conducted in a tenter to obtain a polyamide based laminated biaxial stretching A film was obtained. Then, the properties of the obtained film were evaluated by the same method as in Experimental Example 99. The evaluation results are shown in Tables 17 to 18.

Next, Experimental Examples 103 to 111 relating to the deposited polyamide-based laminated resin film will be described.

[Experimental Example 103]

An unoriented sheet having the following constitution was obtained by using a two-kind three-layer coextrusion T-die apparatus. The total thickness of the unstretched sheet was 190 占 퐉 and the thickness ratio of each layer to the total thickness was 40% / 20% / 40% in the case of the layers B / A / B, , The extrusion resin temperature of the A layer is 270 占 폚, and the extrusion resin temperature of the B layer is 260 占 폚. Composition constituting the A layer: Composition composed of polymethoxy silylene adipamide (manufactured by Mitsubishi Gas Chemical Co., Ltd., RV = 2.65) = 100% by weight. 95% by weight of a composition constituting the layer B: nylon 6 (RV = 2.8, manufactured by Toyo Boseki Co., Ltd.) as a thermoplastic elastomer, a polyamide block copolymer (nylon 12 / polytetramethylene glycol copolymer, Box 4033, RV = 2.0).

The obtained non-stretched sheet was stretched 3.3 times in the longitudinal direction at a stretching temperature of 85 占 폚 by a roll, and then stretched 3.7 times in the transverse direction at a stretching temperature of 120 占 폚 by a tenter. And further heat-set at a temperature of 215 캜, and subjected to a heat relaxation treatment of 5% to prepare a biaxially stretched film having a thickness of 15 탆.

The obtained polyamide-based laminated biaxially stretched film was vapor-deposited in the following manner to produce a vapor-deposited film.

[Aluminum oxide deposition]

On the surface of a polyamide-based resin film constituting the polyamide-based film roll as described above, Al ₂ O ₃ (purity: 99.9%) having a particle size of about 3 to 5 mm was used as an evaporation source, To form an aluminum oxide thin film. As the heating source, EB gun was used, and the emission current was set to 1.3 A. A film having a thickness of 20 nm was formed at a film transfer speed of 130 m / min. The pressure at the time of vapor deposition was adjusted to 1 x 10 < ^-2 > Pa. In addition, the temperature of the roll for cooling the film at the time of vapor deposition was adjusted to -10 캜.

Further, 40 mu m of the surface on which vapor deposition was performed and a linear low-density polyethylene film (L-LDPE film: L6102, Toyo Boseki) were dry-laminated. The oxygen permeability of the obtained laminated film, the number of pinholes after gel-treatment, and the oxygen permeability were measured. The results are shown in Table 19.

[Experimental Example 104]

A biaxially stretched film was obtained in the same manner as in Experimental Example 103 except that the description of Experimental Example 103 was changed as follows.

Composition constituting the B layer: 98% by weight of nylon 6 and 2% by weight of polyamide block copolymer.

The obtained polyamide-based laminated biaxially stretched film was vapor-deposited in the following manner to produce a vapor-deposited film.

[Silicon oxide deposition]

The surface of a polyamide based resin film constituting the polyamide based film roll obtained as described above was produced by using Si (purity: 99.99%) and SiO ₂ (purity: 99.9%) having particle sizes of about 3 to 5 mm as an evaporation source , A silicon oxide thin film was formed by an electron beam evaporation method. The deposition materials were not mixed but were divided into two. As the heating source, an EB gun was used, and each of Si and SiO ₂ was heated in a time division manner. Each material was heated so that the emission current of the EB gun at that time was 0.8 A and the composition ratio of Si and SiO ₂ was 1: 9. A film having a thickness of 20 nm was formed at a film transfer speed of 130 m / min. The pressure at the time of vapor deposition was adjusted to 1 x 10 < ^-2 > Pa. In addition, the temperature of the roll for cooling the film at the time of vapor deposition was adjusted to -10 캜.

The oxygen permeability, the number of pinholes after the gel treatment, and the oxygen permeability of the laminate film obtained in the same manner as in Experimental Example 103 were measured. The results are shown in Table 19.

[Experimental Example 105]

A biaxially stretched film was obtained in the same manner as in Experimental Example 103 except that the description of Experimental Example 103 was changed as follows.

Composition constituting the B layer: a composition comprising 99% by weight of nylon 6 and 1% by weight of a polyamide block copolymer.

The obtained polyamide-based laminated biaxially stretched film was vapor-deposited in the following manner to produce a vapor-deposited film.

[Composite Deposition]

Using a SiO ₂ (purity of 99.9%) and Al ₂ O ₃ (purity of 99.9%) in the form of particles of about 3 mm to 5 mm as an evaporation source, a polyamide based resin film constituting the polyamide based film roll A mixed thin film of aluminum oxide and silicon dioxide was formed by electron beam evaporation. The deposition materials were not mixed but were divided into two. As the heating source, EB gun was used, and each of Al ₂ O ₃ and SiO ₂ was heated by time division. Each material was heated so that the emission current of the EB gun at that time was 1.2 A and the composition ratio of Al ₂ O ₃ and SiO ₂ was 3: 7. A film having a thickness of 20 nm was formed at a film transfer speed of 130 m / min. The pressure at the time of vapor deposition was adjusted to 1 x 10 < ^-2 > Pa. In addition, the temperature of the roll for cooling the film at the time of vapor deposition was adjusted to -10 캜.

The oxygen permeability, the number of pinholes after the gel treatment, and the oxygen permeability of the laminate film obtained in the same manner as in Experimental Example 103 were measured. The results are shown in Table 19.

[Experimental Example 106]

A biaxially stretched film was obtained in the same manner as in Experimental Example 103 except that the description of Experimental Example 103 was changed as follows.

Composition constituting the B layer: 98% by weight of nylon 6 and 2% by weight of polyamide block copolymer.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 41% / 18% / 41%.

The obtained polyamide-based laminated biaxially stretched film was vapor-deposited in the same manner as in Experimental Example 103 to produce a vapor-deposited film.

The oxygen permeability, the number of pinholes after the gel treatment, and the oxygen permeability of the laminate film obtained in the same manner as in Experimental Example 103 were measured. The results are shown in Table 19.

[Experimental Example 107]

A biaxially stretched film was obtained in the same manner as in Experimental Example 103 except that the description of Experimental Example 103 was changed as follows.

Composition constituting the B layer: a composition comprising 97% by weight of nylon 6 and 3% by weight of a polyamide block copolymer.

The thickness ratio of each layer to the total thickness is B layer / A layer / B layer = 39% / 22% / 39%.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 104 to produce an evaporated film.

The oxygen permeability, the number of pinholes after the gel treatment, and the oxygen permeability of the laminate film obtained in the same manner as in Experimental Example 103 were measured. The results are shown in Table 19.

[Test Example 108]

A biaxially stretched film was obtained in the same manner as in Experimental Example 103 except that the description of Experimental Example 103 was changed as follows.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 43% / 14% / 43%.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 105 to produce a vapor-deposited film.

The oxygen permeability, the number of pinholes after the gel treatment, and the oxygen permeability of the laminate film obtained in the same manner as in Experimental Example 103 were measured. The results are shown in Table 19.

[Experimental Example 109]

A biaxially stretched film was obtained in the same manner as in Experimental Example 103 except that the description of Experimental Example 103 was changed as follows.

Composition constituting the B layer: 98% by weight of nylon 6 and 2% by weight of polyamide block copolymer.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 36% / 28% / 36%.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 105 to produce a vapor-deposited film.

The oxygen permeability, the number of pinholes after the gel treatment, and the oxygen permeability of the laminate film obtained in the same manner as in Experimental Example 103 were measured. The results are shown in Table 19.

[Experimental Example 110]

A biaxially stretched film was obtained in the same manner as in Experimental Example 103 except that the description of Experimental Example 103 was changed as follows.

Composition constituting the B layer: a composition comprising 99% by weight of nylon 6 and 1% by weight of a polyamide block copolymer.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 43% / 14% / 43%.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 105 to produce a vapor-deposited film.

The oxygen permeability, the number of pinholes after the gel treatment, and the oxygen permeability of the laminate film obtained in the same manner as in Experimental Example 103 were measured. The results are shown in Table 19.

[Experimental Example 111]

A biaxially stretched film was obtained in the same manner as in Experimental Example 103 except that the description of Experimental Example 103 was changed as follows.

Composition constituting the B layer: a composition comprising 93% by weight of nylon 6 and 7% by weight of a polyamide block copolymer.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 36% / 28% / 36%.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 105 to produce a vapor-deposited film.

The oxygen permeability, the number of pinholes after the gel treatment, and the oxygen permeability of the laminate film obtained in the same manner as in Experimental Example 103 were measured. The results are shown in Table 19.

Comparative Experimental Examples 112 to 117 for Experimental Examples 103 to 111 will be described below.

[Experimental Example 112]

A biaxially stretched film was obtained in the same manner as in Experimental Example 103 except that the description of Experimental Example 103 was changed as follows.

Composition constituting layer B: nylon 6 Composition of 100% by weight.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 105 to produce a vapor-deposited film.

The oxygen permeability, the number of pinholes after the gel treatment, and the oxygen permeability of the laminate film obtained in the same manner as in Experimental Example 103 were measured. The results are shown in Table 19.

[Experimental Example 113]

A biaxially stretched film was obtained in the same manner as in Experimental Example 103 except that the description of Experimental Example 103 was changed as follows.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 30% / 40% / 30%.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 105 to produce a vapor-deposited film.

The oxygen permeability, the number of pinholes after the gel treatment, and the oxygen permeability of the laminate film obtained in the same manner as in Experimental Example 103 were measured. The results are shown in Table 19.

[Experimental Example 114]

A biaxially stretched film was obtained in the same manner as in Experimental Example 103 except that the description of Experimental Example 103 was changed as follows.

Composition constituting Layer A: 80% by weight of polymethylacrylene adipamide and 20% by weight of nylon 6.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 105 to produce a vapor-deposited film.

The oxygen permeability, the number of pinholes after the gel treatment, and the oxygen permeability of the laminate film obtained in the same manner as in Experimental Example 103 were measured. The results are shown in Table 19.

[Experimental Example 115]

A biaxially stretched film was obtained in the same manner as in Experimental Example 103 except that the description of Experimental Example 103 was changed as follows.

Composition constituting Layer A: 80% by weight of polymethylacrylene adipamide and 20% by weight of nylon 6.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 20% / 60% / 20%.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 105 to produce a vapor-deposited film.

The oxygen permeability, the number of pinholes after the gel treatment, and the oxygen permeability of the laminate film obtained in the same manner as in Experimental Example 103 were measured. The results are shown in Table 19.

[Experimental Example 116]

A biaxially stretched film was obtained in the same manner as in Experimental Example 103 except that the description of Experimental Example 103 was changed as follows.

Composition constituting layer A: Composition comprising 90% by weight of polymethoxy silylene adipamide and 10% by weight of polyamide block copolymer.

Composition constituting layer B: nylon 6 Composition of 100% by weight.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 105 to produce a vapor-deposited film.

The oxygen permeability, the number of pinholes after the gel treatment, and the oxygen permeability of the laminate film obtained in the same manner as in Experimental Example 103 were measured. The results are shown in Table 19.

[Experimental Example 117]

A biaxially stretched film was obtained in the same manner as in Experimental Example 103 except that the description of Experimental Example 103 was changed as follows.

Composition constituting layer A: 95% by weight of nylon 6 and 5% by weight of polyamide block copolymer.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 105 to produce a vapor-deposited film.

The oxygen permeability, the number of pinholes after the gel treatment, and the oxygen permeability of the laminate film obtained in the same manner as in Experimental Example 103 were measured. The results are shown in Table 19.

Hereinafter, with respect to Experimental Examples 103 to 111, the peel strength when the vapor-deposited polyamide laminated resin film described in the claims and the laminated film of the polyethylene film having a thickness of 40 占 퐉 were peeled off between the layers was 4.0 N / 15 mm or more Experimental Examples 118 to 129 which are satisfied are described.

[Experimental Example 118]

An unoriented sheet having the following constitution was obtained by using a two-kind three-layer coextrusion T-die apparatus. The total thickness of the unstretched sheet was 190 占 퐉 and the thickness ratio of each layer to the total thickness was 40% / 20% / 40% in the case of the layers B / A / B, , The extrusion resin temperature of the A layer is 270 占 폚, and the extrusion resin temperature of the B layer is 260 占 폚. Composition constituting the A layer: Composition composed of polymethoxy silylene adipamide (manufactured by Mitsubishi Gas Chemical Co., Ltd., RV = 2.65) = 100% by weight. 89% by weight of a composition constituting the B layer: nylon 6 (RV = 2.8, manufactured by Toyo Boseki K.K.) as a thermoplastic elastomer, a polyamide block copolymer (nylon 12 / polytetramethylene glycol copolymer, 5% by weight of polyvinylidene fluoride resin (trade name: Box 4033, RV = 2.0), and 6% by weight of polymethoxy silylene adipamide (manufactured by Mitsubishi Gas Chemical Company, RV = 2.65).

The obtained non-stretched sheet was stretched 3.3 times in the longitudinal direction at a stretching temperature of 85 占 폚 by a roll, and then stretched 3.7 times in the transverse direction at a stretching temperature of 120 占 폚 by a tenter. And further heat-set at a temperature of 215 캜, and subjected to a heat relaxation treatment of 5% to prepare a biaxially stretched film having a thickness of 15 탆.

The obtained polyamide-based laminated biaxially stretched film was vapor-deposited in the following manner to produce a vapor-deposited film.

[Aluminum oxide deposition]

On the surface of the polyamide-based resin film constituting the polyamide-based film roll obtained as described above, Al ₂ O ₃ (purity: 99.9%) having a particle size of about 3 to 5 mm was used as an evaporation source, An aluminum oxide thin film was formed by a vapor deposition method. As the heating source, EB gun was used, and the emission current was set to 1.3 A. A film having a thickness of 20 nm was formed at a film transfer speed of 130 m / min. The pressure at the time of vapor deposition was adjusted to 1 x 10 < ^-2 > Pa. In addition, the temperature of the roll for cooling the film at the time of vapor deposition was adjusted to -10 캜.

Further, 40 mu m of the surface subjected to the vapor deposition treatment and the linear low-density polyethylene film (L-LDPE film: L6102, Toyo Boseki) were dry-laminated. The oxygen permeability of the obtained laminated film, the number of pinholes after gel-treatment, the oxygen permeability, the peel strength and the drop evaluation of the object were evaluated. Table 20 shows the results.

[Experimental Example 119]

A biaxially stretched film was obtained in the same manner as in Example 118 except that the description of Experimental Example 118 was changed as follows.

Composition constituting the layer B: a composition consisting of 95% by weight of nylon 6, 2% by weight of a polyamide block copolymer and 3% by weight of polymethoxy silylene adipamide.

The obtained polyamide-based laminated biaxially stretched film was vapor-deposited in the following manner to produce a vapor-deposited film.

[Silicon oxide deposition]

The surface of the polyamide based resin film constituting the polyamide based film roll obtained as described above was produced by using Si (purity 99.99%) and SiO ₂ (purity 99.9%) having particle sizes of about 3 to 5 mm as an evaporation source , A silicon oxide thin film was formed by an electron beam vapor deposition method. The deposition materials were not mixed but were divided into two. As the heating source, an EB gun was used, and each of Si and SiO ₂ was heated in a time division manner. Each material was heated so that the emission current of EB gun at that time was 0.8 A and the composition ratio of Si and SiO ₂ was 1: 9. A film having a thickness of 20 nm was formed at a film transfer speed of 130 m / min. The pressure at the time of vapor deposition was adjusted to 1 x 10 < ^-2 > Pa. In addition, the temperature of the roll for cooling the film at the time of vapor deposition was adjusted to -10 캜.

The oxygen permeability, the pinhole number, the oxygen permeability, the peel strength, and the fall of the object of the laminated film obtained in the same manner as in Experimental Example 118 were measured. Table 20 shows the results.

[Experimental Example 120]

A biaxially stretched film was obtained in the same manner as in Example 118 except that the description of Experimental Example 118 was changed as follows.

Composition constituting the B layer: a composition comprising 97% by weight of nylon 6, 1% by weight of a polyamide block copolymer, and 2% by weight of polymethoxy silylene adipamide.

The obtained polyamide-based laminated biaxially stretched film was vapor-deposited in the following manner to produce a vapor-deposited film.

[Composite Deposition]

Using a SiO ₂ (purity of 99.9%) and Al ₂ O ₃ (purity of 99.9%) in the form of particles of about 3 mm to 5 mm as an evaporation source, a polyamide based resin film constituting the polyamide based film roll A mixed thin film of aluminum oxide and silicon dioxide was formed by electron beam evaporation. The deposition materials were not mixed but were divided into two. As the heating source, EB gun was used, and each of Al ₂ O ₃ and SiO ₂ was heated by time division. Each material was heated so that the emission current of the EB gun at that time was 1.2 A and the composition ratio of Al ₂ O ₃ and SiO ₂ was 3: 7. A film having a thickness of 20 nm was formed at a film transfer speed of 130 m / min. The pressure at the time of vapor deposition was adjusted to 1 x 10 < ^-2 > Pa. In addition, the temperature of the roll for cooling the film at the time of vapor deposition was adjusted to -10 캜.

The oxygen permeability, the pinhole number, the oxygen permeability, the peel strength, and the fall of the object of the laminated film obtained in the same manner as in Experimental Example 118 were measured. Table 20 shows the results.

[Experimental Example 121]

A biaxially stretched film was obtained in the same manner as in Example 118 except that the description of Experimental Example 118 was changed as follows.

Composition constituting the B layer: a composition consisting of 95% by weight of nylon 6, 2% by weight of polyamide block copolymer and 3% by weight of polymethylacrylene adipamide.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 41% / 18% / 41%.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 118 to produce an evaporated film.

The oxygen permeability, the pinhole number, the oxygen permeability, the peel strength, and the fall of the object of the laminated film obtained in the same manner as in Experimental Example 118 were measured. Table 20 shows the results.

[Experimental Example 122]

A biaxially stretched film was obtained in the same manner as in Example 118 except that the description of Experimental Example 118 was changed as follows.

Composition comprising B layer: 92% by weight of nylon 6, 3% by weight of polyamide block copolymer and 5% by weight of polymethylacrylene adipamide.

The thickness ratio of each layer to the total thickness is B layer / A layer / B layer = 39% / 22% / 39%.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 119 to produce an evaporated film.

The oxygen permeability, the pinhole number, the oxygen permeability, the peel strength, and the fall of the object of the laminated film obtained in the same manner as in Experimental Example 118 were measured. Table 20 shows the results.

[Experimental Example 123]

A biaxially stretched film was obtained in the same manner as in Example 118 except that the description of Experimental Example 118 was changed as follows.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 43% / 14% / 43%.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 120 to produce an evaporated film.

The oxygen permeability, the pinhole number, the oxygen permeability, the peel strength, and the fall of the object of the laminated film obtained in the same manner as in Experimental Example 118 were measured. Table 20 shows the results.

[Experimental Example 124]

A biaxially stretched film was obtained in the same manner as in Example 118 except that the description of Experimental Example 118 was changed as follows.

Composition constituting the layer B: a composition consisting of 95% by weight of nylon 6, 2% by weight of a polyamide block copolymer and 3% by weight of polymethoxy silylene adipamide. The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 36% / 28% / 36%.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 120 to produce an evaporated film.

The oxygen permeability, the pinhole number, the oxygen permeability, the peel strength, and the fall of the object of the laminated film obtained in the same manner as in Experimental Example 118 were measured. Table 20 shows the results.

[Experimental Example 125]

A biaxially stretched film was obtained in the same manner as in Example 118 except that the description of Experimental Example 118 was changed as follows.

Composition constituting the B layer: a composition comprising 97% by weight of nylon 6, 1% by weight of a polyamide block copolymer, and 2% by weight of polymethoxy silylene adipamide.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 43% / 14% / 43%.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 120 to produce an evaporated film.

The oxygen permeability, the pinhole number, the oxygen permeability, the peel strength, and the fall of the object of the laminated film obtained in the same manner as in Experimental Example 118 were measured. Table 20 shows the results.

[Experimental Example 126]

A biaxially stretched film was obtained in the same manner as in Example 118 except that the description of Experimental Example 118 was changed as follows.

Composition constituting the B layer: Composition composed of 83% by weight of nylon 6, 7% by weight of polyamide block copolymer and 10% by weight of polymethoxy silylene adipamide.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 36% / 28% / 36%.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 120 to produce an evaporated film.

The oxygen permeability, the pinhole number, the oxygen permeability, the peel strength, and the fall of the object of the laminated film obtained in the same manner as in Experimental Example 118 were measured. Table 20 shows the results.

[Experimental Example 127]

A biaxially stretched film was obtained in the same manner as in Example 118 except that the description of Experimental Example 118 was changed as follows.

Composition constituting the B layer: a composition consisting of 93% by weight of nylon 6, 5% by weight of a polyamide block copolymer and 2% by weight of polymethoxy silylene adipamide.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 120 to produce an evaporated film.

The oxygen permeability, the pinhole number, the oxygen permeability, the peel strength, and the fall of the object of the laminated film obtained in the same manner as in Experimental Example 118 were measured. Table 20 shows the results.

[Experimental Example 128]

A biaxially stretched film was obtained in the same manner as in Example 118 except that the description of Experimental Example 118 was changed as follows.

Composition comprising B layer: 84% by weight of nylon 6, 5% by weight of polyamide block copolymer and 11% by weight of polymethoxy silylene adipamide.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 120 to produce an evaporated film.

The oxygen permeability, the pinhole number, the oxygen permeability, the peel strength, and the fall of the object of the laminated film obtained in the same manner as in Experimental Example 118 were measured. Table 20 shows the results.

Comparative Experiments 130 to 139 for Experiments 118 to 129 will be described below.

[Experimental Example 129]

A biaxially stretched film was obtained in the same manner as in Example 118 except that the description of Experimental Example 118 was changed as follows.

Composition constituting the B layer: a composition consisting of 98% by weight of nylon 6, 1% by weight of a polyamide block copolymer and 1% by weight of polymethoxy silylene adipamide.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 120 to produce an evaporated film.

The oxygen permeability, the pinhole number, the oxygen permeability, the peel strength, and the fall of the object of the laminated film obtained in the same manner as in Experimental Example 118 were measured. Table 20 shows the results.

[Experimental Example 130]

A biaxially stretched film was obtained in the same manner as in Example 118 except that the description of Experimental Example 118 was changed as follows.

Composition constituting layer B: nylon 6 Composition of 100% by weight.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 120 to produce an evaporated film.

The oxygen permeability, the pinhole number, the oxygen permeability, the peel strength, and the fall of the object of the laminated film obtained in the same manner as in Experimental Example 118 were measured. Table 20 shows the results.

[Experimental Example 131]

A biaxially stretched film was obtained in the same manner as in Example 118 except that the description of Experimental Example 118 was changed as follows.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 30% / 40% / 30%.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 120 to produce an evaporated film.

The oxygen permeability, the pinhole number, the oxygen permeability, the peel strength, and the fall of the object of the laminated film obtained in the same manner as in Experimental Example 118 were measured. Table 20 shows the results.

[Experimental Example 132]

A biaxially stretched film was obtained in the same manner as in Example 118 except that the description of Experimental Example 118 was changed as follows.

Composition constituting Layer A: 80% by weight of polymethylacrylene adipamide and 20% by weight of nylon 6.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 120 to produce an evaporated film.

The oxygen permeability, the pinhole number, the oxygen permeability, the peel strength, and the fall of the object of the laminated film obtained in the same manner as in Experimental Example 118 were measured. Table 20 shows the results.

[Experimental Example 133]

A biaxially stretched film was obtained in the same manner as in Example 118 except that the description of Experimental Example 118 was changed as follows.

Composition constituting Layer A: 80% by weight of polymethylacrylene adipamide and 20% by weight of nylon 6.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 20% / 60% / 20%.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 120 to produce an evaporated film.

The oxygen permeability, the pinhole number, the oxygen permeability, the peel strength, and the fall of the object of the laminated film obtained in the same manner as in Experimental Example 118 were measured. Table 20 shows the results.

[Experimental Example 134]

A biaxially stretched film was obtained in the same manner as in Example 118 except that the description of Experimental Example 118 was changed as follows.

Composition constituting Layer A: 80% by weight of polymethylacrylene adipamide and 20% by weight of nylon 6.

The ratio of the thickness of each layer to the total thickness is B layer / A layer / B layer = 30% / 40% / 30%.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 120 to produce an evaporated film.

The oxygen permeability, the pinhole number, the oxygen permeability, the peel strength, and the fall of the object of the laminated film obtained in the same manner as in Experimental Example 118 were measured. Table 20 shows the results.

[Experimental Example 135]

A biaxially stretched film was obtained in the same manner as in Example 118 except that the description of Experimental Example 118 was changed as follows.

Composition constituting the B layer: a composition comprising 95% by weight of nylon 6 and 5% by weight of a polyamide block copolymer.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 120 to produce an evaporated film.

The oxygen permeability, the pinhole number, the oxygen permeability, the peel strength, and the fall of the object of the laminated film obtained in the same manner as in Experimental Example 118 were measured. Table 20 shows the results.

[Experimental Example 136]

A biaxially stretched film was obtained in the same manner as in Example 118 except that the description of Experimental Example 118 was changed as follows.

Composition constituting the B layer: a composition comprising 99% by weight of nylon 6 and 1% by weight of a polyamide block copolymer.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 120 to produce an evaporated film.

The oxygen permeability, the pinhole number, the oxygen permeability, the peel strength, and the fall of the object of the laminated film obtained in the same manner as in Experimental Example 118 were measured. Table 20 shows the results.

[Experimental Example 137]

A biaxially stretched film was obtained in the same manner as in Example 118 except that the description of Experimental Example 118 was changed as follows.

Composition comprising B layer: 95% by weight of nylon 6 and 5% by weight of polymethoxy silylene adipamide.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 120 to produce an evaporated film.

The oxygen permeability, the pinhole number, the oxygen permeability, the peel strength, and the fall of the object of the laminated film obtained in the same manner as in Experimental Example 118 were measured. Table 20 shows the results.

[Experimental Example 138]

A biaxially stretched film was obtained in the same manner as in Example 118 except that the description of Experimental Example 118 was changed as follows.

Composition constituting layer A: Composition comprising 90% by weight of polymethoxy silylene adipamide and 10% by weight of polyamide block copolymer.

Composition constituting layer B: nylon 6 Composition of 100% by weight.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 120 to produce an evaporated film.

The oxygen permeability, the pinhole number, the oxygen permeability, the peel strength, and the fall of the object of the laminated film obtained in the same manner as in Experimental Example 118 were measured. Table 20 shows the results.

[Experimental Example 139]

A biaxially stretched film was obtained in the same manner as in Example 118 except that the description of Experimental Example 118 was changed as follows.

Composition constituting layer A: 95% by weight of nylon 6 and 5% by weight of polyamide block copolymer.

Composition constituting the B layer: a composition comprising 95% by weight of nylon 6 and 5% by weight of a polyamide block copolymer.

The obtained polyamide-based laminated biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 120 to produce an evaporated film.

The oxygen permeability, the pinhole number, the oxygen permeability, the peel strength, and the fall of the object of the laminated film obtained in the same manner as in Experimental Example 118 were measured. Table 20 shows the results.

Industrial availability

The polyamide-based laminated biaxially stretched film and the deposited polyamide-based laminated resin film of the present invention have excellent oxygen gas barrier properties and are excellent in impact resistance and flexural fatigue resistance, and are useful for preventing deterioration of contents or discoloration And the content can be protected from bending fatigue caused by impact or vibration during transportation, and can be effectively used as various packaging materials.

Brief Description of Drawings

Fig. 1 is an explanatory view showing a state of shielding by a conventional shielding plate (a shows a vertical section of a part of a heat fixing device, and b shows a state in which a shielding plate is attached to a hot air blowout opening of a plenum duct, will be).

Fig. 2 is an explanatory view showing a state of shielding by a shielding plate in the present invention (a shows a vertical section of a part of a heat fixing device, and b shows a state in which a shielding plate is attached to a hot air blowout opening of a plenum duct, This state is shown).

Fig. 3 is an explanatory view showing a state in which the open and closed clothes used in the experimental example are viewed from above. Fig.

4 is an explanatory diagram showing a shielding mode by shielding plates in Experimental Examples 43 and 51;

5 is an explanatory diagram showing a state in which electrodes are disposed on the moving cooling body to perform streamer corona discharge.

1: heat fixing device
2: Hot air blow out port
3, a to x: plenum duct
F: Film
S: Shield plate
11: Dice
12: Sheet-like melt
13: Cooling drum
14: Undeveloped sheet
15: DC high voltage power source
16: Electrode
17: Streamer corona discharge

Claims (15)

Aliphatic dicarboxylic acid component having 6 to 12 carbon atoms as a main diamine component is mixed with a main dicarboxylic acid component, (B layer) composed mainly of an aliphatic polyamide resin is laminated on both sides of a resin layer (A layer) composed mainly of a methacrylic acid group-containing polyamide polymer composed of a tetracarboxylic acid component, Wherein the thickness of the A layer is 10% or more and 25% or less of the total thickness of the A layer and the B layer, and the following requirements (1) to (3) are satisfied: Wherein the polyamide-based laminated biaxially stretched film is satisfactory.
(1) the ratio of the meta-xylylene group-containing polyamide polymer in the resin layer (A layer) containing the above-mentioned meta-xylylene group-containing polyamide polymer as a main component is not less than 99% by weight and the thermoplastic elastomer is not added, Is added in a proportion of less than 1% by weight
(2) The laminate film of the polyamide-based laminated biaxially stretched film and the polyethylene film having a thickness of 40 占 퐉 was continuously fed at a rate of 40 cycles per minute in an atmosphere of a temperature of 23 占 폚 and a relative humidity of 50% using a gelboplex tester The number of pinholes when the bending test is performed for 2000 cycles is 10 or less
(3) The oxygen permeability at a temperature of 23 ° C and a relative humidity of 65% is 150 ml / m 2 · MPa · day or less The method according to claim 1,
Wherein the laminated biaxially stretched polyamide laminate film and the laminated film of a polyethylene film having a thickness of 40 占 퐉 have a peel strength of 4.0 N / 15 mm or more when they are peeled from each other between the layers. The method according to claim 1,
Wherein the thermoplastic elastomer is added to the resin layer (B layer) composed mainly of the aliphatic polyamide resin so that the blend ratio of the thermoplastic elastomer is 0.5 wt% to 8.0 wt%. 3. The method of claim 2,
A mixture of a thermoplastic elastomer in an amount of not less than 0.5% by weight and not more than 8.0% by weight and a methacrylic group-containing polyamide polymer in an amount of not less than 1.0% by weight and not more than 12.0% by weight in a resin layer (B layer) composed mainly of the aliphatic polyamide resin By weight of the polyamide-based laminated biaxially stretched film. 3. The method according to claim 1 or 2,
Wherein the polyamide-based laminated biaxially stretched film satisfies the following formula (I).

(Where x is the content (wt%) of the methacrylic group-containing polyamide polymer in the film, Pa is the oxygen permeability (ml / m 2 · MPa · day) of the film at a temperature of 23 ° C. and a relative humidity of 65% Represents the thickness (mm) of the film. 3. The method according to claim 1 or 2,
Wherein the thickness of the A layer is 10% or more and 30% or less of the total thickness of the A layer and the B layer. 3. The method according to claim 1 or 2,
(4) and (5) satisfying the following requirements (4) and (5), wherein DELTA nab, which is a difference between a refractive index in a direction forming an angle of 45 degrees with the winding direction of the film and a refractive index in a direction forming an angle of 135 DEG, Wherein the polyamide-based laminated biaxially stretched film is a polyamide-based laminated biaxially stretched film.
(4) For a film having a length in the width direction of the film of 80 cm or more, five samples were evenly divided in the width direction of the film, and five samples cut from the center in the width direction of each of the five When the difference between the maximum value and the minimum value of the HS160 is found, the difference is 0.15% or less when the HS160, which is the heat shrinkage rate in the film winding direction when heated for 10 minutes, is obtained.
(5) For all of the above five samples, HS160 should be 0.5% or more and 2.0% or less 3. The method according to claim 1 or 2,
Wherein the thickness unevenness is in the range of 3 to 10%. 3. The method according to claim 1 or 2,
Characterized in that at least one surface of the film has an outermost surface coated with an adhesive modifying resin made of a copolymerized polyester. An evaporated polyamide laminate resin film characterized in that an inorganic material is deposited on at least one side of the polyamide based laminated biaxially stretched film according to claim 1 and satisfies the following requirements (9) to (12).
(9) The thermoplastic resin composition according to any one of the above items (1) to (3), wherein the ratio of the meta-xylylene group-containing polyamide polymer in the resin layer (A layer) comprising the methacryl- Is added in a proportion of less than 1% by weight
(10) The laminated film of the deposited polyamide-based laminated resin film and the polyethylene film having a thickness of 40 탆 was continuously fed at a rate of 40 cycles per minute in an atmosphere of a temperature of 23 캜 and a relative humidity of 50% using a gelboplex tester The number of pinholes when the bending test is performed for 2000 cycles is 10 or less
(11) The oxygen transmission rate of the laminated film of the deposited polyamide-based laminated resin film and the polyethylene film having a thickness of 40 占 퐉 at a temperature of 23 占 폚 and a relative humidity of 65% is 50 ml / m.sup.2.multidot.day day or less.
(12) The laminated film of the deposited polyamide-based laminated resin film and the polyethylene film having a thickness of 40 탆 was continuously fed at a rate of 40 cycles per minute in an atmosphere of a temperature of 23 캜 and a relative humidity of 50% using a gelboplex tester , The oxygen permeability at a temperature of 23 캜 and a relative humidity of 65% is 100 ml / m 2 · MPa · day or less 11. The method of claim 10,
Wherein the peel strength when the laminated film of the deposited polyamide laminated resin film and the laminated film of the polyethylene film having a thickness of 40 탆 is peeled off between the layers is 4.0 N / 15 mm or more. 11. The method of claim 10,
Wherein the thermoplastic elastomer is added in a resin layer (B layer) composed mainly of the aliphatic polyamide resin so that the blend ratio of the thermoplastic elastomer is 0.5 wt% or more and 8.0 wt% or less. 12. The method of claim 11,
A mixture of a thermoplastic elastomer in an amount of not less than 0.5% by weight and not more than 8.0% by weight and a methacrylic group-containing polyamide polymer in an amount of not less than 1.0% by weight and not more than 12.0% by weight in a resin layer (B layer) composed mainly of the aliphatic polyamide resin By weight based on the total weight of the polyamide-based laminated resin film. The method according to claim 10 or 11,
Wherein the thickness of the A layer is 10% or more and 30% or less of the total thickness of the A layer and the B layer. The method according to claim 10 or 11,
Wherein the inorganic material is one or more metals or nonmetals selected from aluminum, silicon, titanium, magnesium, zirconium, cerium, tin, copper, iron and zinc or an oxide, nitride, fluoride or sulfide of said metal or non- Lt; RTI ID = 0.0 > polyamide < / RTI >

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